WO2001053375A1 - Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same - Google Patents

Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same Download PDF

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Publication number
WO2001053375A1
WO2001053375A1 PCT/JP2001/000268 JP0100268W WO0153375A1 WO 2001053375 A1 WO2001053375 A1 WO 2001053375A1 JP 0100268 W JP0100268 W JP 0100268W WO 0153375 A1 WO0153375 A1 WO 0153375A1
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group
general formula
epoxy compound
polynuclear
epoxy
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PCT/JP2001/000268
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French (fr)
Japanese (ja)
Inventor
Noboru Kohiyama
Shoji Minegishi
Tadahiro Miyoshi
Hiromitsu Morino
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Taiyo Ink Manufacturing Co., Ltd.
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Priority claimed from JP2000090931A external-priority patent/JP3723036B2/en
Application filed by Taiyo Ink Manufacturing Co., Ltd. filed Critical Taiyo Ink Manufacturing Co., Ltd.
Publication of WO2001053375A1 publication Critical patent/WO2001053375A1/en

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    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F269/00—Macromolecular compounds obtained by polymerising monomers on to polymers of heterocyclic oxygen-containing monomers as defined in group C08F24/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • H05K3/4676—Single layer compositions

Definitions

  • the present invention relates to a novel linear polynuclear epoxy compound containing different aromatic rings regularly and repeatedly, a polynuclear epoxy acrylate compound derived from the polynuclear epoxy compound, and a curable resin composition containing the same.
  • the present invention also relates to a novel, linearly soluble, active energy ray-curable resin derived from the above-mentioned polynuclear epoxy compound or polynuclear epoxy acrylate compound.
  • the present invention relates to a photo-curable and thermo-curable resin composition which can be developed in liquid form using the active energy ray-curable resin and a cured film forming technique using the same.
  • Epoxy resins typified by bisphenol A-type epoxy resins have excellent adhesiveness, heat resistance, chemical resistance, and electrical insulation, and have been widely used for adhesives, casting agents, laminates, paints, Used for applications such as sealants.
  • polynuclear epoxy resins such as cresol nopolak epoxy resin and phenol novolak epoxy resin have been proposed as epoxy compounds having excellent heat resistance.
  • these epoxy resins are certainly excellent in heat resistance, they have a disadvantage that they tend to crack easily due to thermal shock because of their large shrinkage upon curing, low elongation, and lack of toughness.
  • a method for solving the above-mentioned drawbacks a method of blending a rubber component into an epoxy resin (Japanese Patent Application Laid-Open No. Sho 63-1991) and a method of blending two types of epoxy resins are disclosed.
  • Japanese Patent No. 27831116 Japanese Patent Application Laid-Open No. Sho 63-1991
  • a copolymerized epoxy resin of a biphenyl skeleton and a bisphenol skeleton Japanese Patent No. 2789325
  • epoxy (meth) acrylates derived from polyhydric phenol-type epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy resins and (meth) acrylic acid Radical polymerization type resins such as acrylates or unsaturated polyesters are known.
  • these resins contain a radical polymerization crosslinker such as styrene and are widely used as vinyl ester resins or unsaturated polyester resins. It has been done.
  • these resins do not always reach a satisfactory level in terms of thermal stability at high temperatures, and have large shrinkage during curing, low elongation, and lack in toughness. There was a drawback that it was easy to do.
  • a modified aromatic amine, a polymerizable cross-linking agent, and a bus phenyl acrylonitrile copolymer having an acryloyl group and / or a methyl acryloyl group are used.
  • a resin composition comprising a modified aromatic polyamine and / or a modified aromatic diamine, an epoxy compound, and a radical polymerizable crosslinking agent (Japanese Patent Application Laid-Open No. No. 2997442).
  • these methods are still insufficient to satisfy both heat resistance and toughness.
  • solder resists of some commercial printed wiring boards and most industrial printed wiring boards have been developed from the viewpoint of high precision and high density by forming an image by irradiating ultraviolet rays and developing them.
  • a liquid development type solder resist that performs final curing (final curing) by light irradiation is used.
  • Liquid soldering resists of the developing type using a dilute aqueous solution as a developing solution are mainly used.
  • Sho 61-224439 discloses a novolak type epoxy compound and an unsaturated A solder resist composition
  • a photosensitive resin obtained by adding an acid anhydride to a reaction product of a basic acid, a photopolymerization initiator, a diluent, and an epoxide compound is disclosed in Japanese Patent Application Laid-Open No. 3-253930.
  • the publications include a photosensitive resin in which an acid anhydride is added to the reaction product of a novolak epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, a mixture of vinyltriazine or vinyltriazine and dicyandiamide, and A solder resist composition comprising a melamine resin is disclosed.
  • Such a photosensitive resin is excellent in photocurability and alkali developability, but is not necessarily at a satisfactory level in terms of thermal stability at high temperatures. It has a disadvantage that it tends to shrink, has low elongation, and lacks toughness, so that cracks easily occur due to thermal shock.
  • solder packages have been replaced by IC packages called lead-frame and encapsulating resin, such as QFP (quad 'flat-knock' package) and SOP (small 'outline' package).
  • QFP quad 'flat-knock' package
  • SOP small 'outline' package
  • Ball-shaped solder or other metal is arranged in an area on one side of the printed printed wiring board, and an IC chip is directly connected to the other side by wire bonding or bumping, and sealed with a sealing resin.
  • IC packages with such a structure have appeared, and are called by names such as BGA (ball 'grid' array) and CSP (chip 'scale package').
  • the present invention has been made in view of the above circumstances, and one of its objects is to provide well-balanced heat resistance and toughness, as well as adhesion to a substrate, water resistance, chemical resistance, and electrical insulation.
  • An object of the present invention is to provide a polynuclear epoxy compound having excellent moldability and good moldability, and a thermosetting resin composition containing the same.
  • Another object of the present invention is to provide a polynuclear epoxy acrylate compound derived from a polynuclear epoxy compound having the above-described excellent properties and capable of being cured by both irradiation with active energy rays and heat. It is an object of the present invention to provide a curable resin composition.
  • Another object of the present invention is to provide an active energy ray-curable resin which has excellent heat stability at high temperatures, has well-balanced heat resistance and toughness, and also has excellent photocurability and high reversibility developability. Is to do.
  • Still another object of the present invention is to provide a conventional solder resist for a printed wiring board and heat resistance, adhesion, electroless plating resistance, electrical characteristics, and flexibility required for an interlayer insulating layer of a multilayer wiring board. And other properties, and a cured film with excellent properties such as moisture absorption resistance and PCT (pressure cooker) resistance required especially for IC packages can be obtained. It is an object of the present invention to provide a liquid photocurable / thermosetting resin composition which can be developed and can be developed completely. Disclosure of the invention
  • X and Y represent different aromatic groups, and X is selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether.
  • the polynuclear epoxy compound of the present invention as described above is a linear polynuclear epoxy compound containing different aromatic rings regularly and repeatedly, particularly a biphenyl skeleton and a naphthylene skeleton or a bisphenol skeleton having a high softening point. And a naphthylene skeleton are alternately copolymerized, so that the cured product of the polynuclear epoxy compound has a high level of heat resistance and toughness balance, and Excellent adhesion to materials and excellent water resistance, chemical resistance, electrical insulation, etc.
  • a polynuclear epoxy acrylate compound (b) represented by the following general formula (2a) or (2b) and a curable resin composition containing the same. Is done.
  • X, Y and n have the same meanings as described above, and Z independently of one another represents a group represented by the following general formula (3) or (4) or a hydrogen atom, and at least one of Z Is a group represented by the general formula (3), and Z, independently of each other, represents a group represented by the following general formula (3,) or (4,).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an unsaturated monocarboxylic acid residue
  • a reaction product (b,) of a polynuclear epoxy compound (a,) represented by the following general formula (5) and a monocarboxylic acid containing an unsaturated group (c) is polybasic:
  • An active energy ray-curable resin obtained by reacting the acid anhydride (d) is provided.
  • X 3 and Y represent different divalent aromatic rings
  • ⁇ represents a glycidyl group and / or a hydrogen atom
  • ⁇ represents an integer of 1 to 20.
  • the mixing ratio of each component is not limited to a specific ratio, but ( ⁇ ) 100 parts by mass of the active energy ray-curable resin, and ( ⁇ ) the photosensitive (meth) methacrylate compound in 10 to 10 parts by mass. 60 parts by mass, preferably 15 to 50 parts by mass, (C) 0.1 to 25 parts by mass of the photopolymerization initiator, preferably 0.5 to 20 parts by mass, and (D) the polyfunctional epoxy compound. It is preferable to use the epoxy curing catalyst in a ratio of 0.1 to 20 parts by mass, more preferably 100 to 100 parts by mass, and if necessary ( ⁇ ).
  • the photocurable and thermosetting resin composition of the present invention containing such an active energy ray-curable resin as a photocurable component has a photocurable property, an alkali developable property and an adhesive property to a substrate.
  • the cured product is excellent in heat resistance, water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexibility, PCT resistance, etc ..
  • FIG. 1 is an infrared absorption spectrum of the polynuclear epoxy compound (a-2) obtained in Synthesis Example 2;
  • FIG. 2 is a nuclear magnetic resonance spectrum of the polynuclear epoxy compound (a-2) obtained in Synthesis Example 2;
  • FIG. 3 is an infrared absorption spectrum of the polynuclear epoxy acrylate compound (b-1) obtained in Synthesis Example 8;
  • FIG. 6 is a nuclear magnetic resonance spectrum of the active energy linear curable resin (A-1) obtained in Synthesis Example 14. BEST MODE FOR CARRYING OUT THE INVENTION
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, as a result, a linear epoxy compound containing regularly different kinds of aromatic rings represented by X and Y, particularly having a high softening point.
  • a polynuclear C-epoxy compound obtained by reacting an alcoholic hydroxyl group in an H compound with an epihalohydrin is a cured product that has both excellent heat resistance and toughness
  • the polynuclear epoxy compound (a) of the present invention contains a different type of aromatic ring regularly and repeatedly, so that a cured product having high mechanical strength can be obtained.
  • a cured product with high mechanical strength can be obtained.
  • a cured product with high heat resistance can be obtained, as well as adhesion to substrates, water resistance, chemical resistance, and electricity.
  • a cured product having excellent insulation properties and moldability can be obtained.
  • X and Y represent different aromatic rings, and X is at least one selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether.
  • Each represents an aromatic ring residue of an aromatic epoxide compound having two glycidyl groups in one molecule
  • ⁇ represents dihydroxynaphthylene and its derivative, biphenyl and its derivative, bixylenol and
  • the aromatic residue of an aromatic alcohol having at least two phenolic hydroxyl groups in one molecule selected from the group consisting of its derivatives, bisphenol and its derivatives, and hydroquinone and its derivatives Represents a glycidyl group and / or a hydrogen atom, and ⁇ represents an integer of 1 to 20.
  • the above-mentioned polynuclear epoxy compound can be produced by various methods.
  • Polynuclear epoxy compounds obtained by reacting with drin 2 o are preferred, and are relatively easy to produce.
  • a more specific preferred embodiment is the following general formula (8a) or (8a) obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (7a) or (7b) with ephalohydrin It is a polynuclear epoxy compound represented by (8b).
  • R 3 , R 4 , 5 , R 6 are the same or different, are each a hydrogen atom or carbon
  • R 3 to R 6 are all hydrogen atoms or R 6 3 to R S are all methyl groups, and: R 7 to R 10 are all hydrogen atoms, R 11 and R 12 are all methyl groups, while divalent naphthylene ring residue is 1 , 5—, 1, 6—, 2, 6— or 2,7—substituted.
  • R 3 to R 6 are all methyl groups, and the divalent naphthalene ring residue is a 1,5-, 1,6- or 2,6-substituted product .
  • the yield of epoxidation by hydrin hydrin decreases as the number average molecular weight of the epoxy compound represented by the general formula (6) increases.
  • the alcoholic hydroxyl groups can be epoxidized at a desired ratio by adjusting the amount of the metal hydroxide as a catalyst.
  • the epoxy compound represented by the general formula (6) includes an aromatic epoxy compound having two glycidyl groups in one molecule (hereinafter referred to as a bifunctional aromatic epoxy compound) and two epoxy compounds in one molecule.
  • a bifunctional aromatic epoxy compound an aromatic epoxy compound having two glycidyl groups in one molecule
  • polymerization is carried out alternately in a solvent or in the absence of a solvent, using a known esterification catalyst as described below. It can be easily manufactured by the method.
  • bifunctional aromatic epoxy compound examples include biphenyl-type diglycidyl ethers having aromatic rings represented by the following formulas (A) to (D), bixylenol-type diglycidyl ethers, bisphenol-type diglycidyl ethers and the like. At least one bifunctional aromatic epoxy compound selected from the group consisting of naphthylene-diglycidyl ethers is preferably used.
  • a bifunctional aromatic epoxy compound as one monomer component in an alternating copolymer with a bifunctional aromatic alcohol, a polynuclear compound excellent in strength, heat resistance, electrical insulation, etc. of a cured product is obtained. An epoxy compound is obtained.
  • R 3 , R 4 S R 5 and R 6 are the same or different from each other
  • R 7 , R 8 , and RR 1 Q represent the same or different hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or halogen atoms
  • R 1 R 12 represents Represents the same or different hydrogen atom, methyl group or methyl halide group.
  • Examples of the biglycol type, bixylenol type, bisphenol type or naphthalene type diglycidyl ether include, for example, a biphenol compound, a bixylenol compound, a bisphenol compound, or a reaction between dihydroxynaphthalene and epihalohydrin. What is manufactured can be used. In addition, commercially available epoxy compounds can also be used. Examples of the biphenyl-type diglycidyl ethers include “Epicoat YL-6056” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). As a diglycidyl ether type, such as "Epicoat YX-400" manufactured by Japan Epoxy Resin Co., Ltd.
  • the bifunctional aromatic alcohol used in the present invention has a feature in its structure.
  • An alcohol having an aromatic ring in order to enhance heat resistance and having a symmetrical structure or a rigid structure can be used.
  • Such compounds include, for example, 1,4-dihydroxyxafene, 1,5-dihydroxyxafene, 1,6-dihydroxyxafene, 2,6-dihydroxyxafene, 2,7— Dihydroxy naphthalene derivatives such as dihydroxy synafene, 2,8-dihydroxy naphthene, biphenol derivatives such as bixylenol and biphenol, and bisphenol Bisphenol derivatives such as phenol 8, bisphenol 5 ⁇ bisphenol S, alkyl-substituted bisphenol, and hydroquinone derivatives such as hydroquinone, methylhydroquinone, and trimethylhydroquinone.
  • the epoxy compound represented by the general formula (7a) or (7b) includes a biphenyl-type and a Z- or bixylenol-type epoxy compound or a bisphenol-type epoxy compound; , 6,2,6-, 2,7-substituted and at least one dihydroxynaphthylene is used as a raw material and an etherification catalyst is used to alternately polymerize in a solvent or without a solvent.
  • dihydroxyxina and phthalene it is preferable to use 1,5-, 1,6- or 2,6-substituted compounds having a high softening point, particularly symmetric 1,5- and 2,6-substituted products.
  • Examples of the catalyst used for the synthesis of the epoxy compounds represented by the general formulas (6), (7a), and (7b) include phosphines, alkali metal compounds, and glycidyl groups that react quantitatively with phenolic hydroxyl groups. It is preferable to use amines alone or in combination. Other catalysts are not preferable because they cause gelation.
  • phosphines examples include trialkyl or triaryl phosphines such as tributyl phosphine and triphenyl phosphine, and salts of these with an acid compound.
  • alkali metal compound examples include hydroxides, halides, alcoholates, and amides of alkali metals such as sodium, lithium, and potassium, and these can be used alone or in combination of two or more. .
  • amines examples include aliphatic or aromatic primary, secondary, tertiary, and quaternary amines. These may be used alone or in combination of two or more. Can be. Specific examples of amines include triethanolamine, N, N-dimethylbiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramamine, pyridine, tetramethylammonium bromide and the like. .
  • These catalysts are used in an amount of 0.001 to 1 part by mass, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol. It is preferably used in the range of parts. The reason for this is that if the amount of catalyst used is less than 0.001 parts by mass, the reaction takes a long time and is not economical, whereas if it exceeds 1 part by mass, the reaction is too fast to control. Because it becomes.
  • the reaction between the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol is preferably carried out in the presence of the catalyst in a stream of inert gas or in air at a temperature in the range of 130 to 180 ° C.
  • the polynuclear epoxy compound of the present invention represented by the general formula (1) or (8a) or (8b) may be used in a known solvent or in the absence of a solvent as described below in the presence of an alkali metal hydroxide.
  • the compound can be produced by reacting an alcoholic hydroxyl group in the epoxy compound of the general formula (6) or (7a) or (7b) with ephalohydrin.
  • the epihalohydrin for example, ebichlorhydrin, epibihydr muhydrin, epiohydrin, 1-methylepichlorohydrin, -methylepibromhydrin, 5-methylepihydrhydrin and the like are used.
  • the amount of ephalohydrin used may be the general formula (6) or (7a), (7b) May be used in an amount of 0.1 equivalent or more per equivalent of the alcoholic hydroxyl group in the above.
  • the use of an amount exceeding 15 equivalents to 1 equivalent of the hydroxyl group is not preferable because the volumetric efficiency is deteriorated.
  • the solvent examples include non-protonic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and known solvents such as aromatic hydrocarbons such as toluene and xylene. Among them, a non-protonic polar solvent, particularly, dimethyl sulfoxide is preferable.
  • the amount of the solvent used is preferably 5 to 300% by mass based on the epoxy compound represented by the general formula (6) or (7a) or (7b). The reason for this is that if it is less than 5% by mass, the reaction between the alcoholic hydroxyl group and the ephalohydrin will be slow, while if it exceeds 300% by mass, the volumetric efficiency will be poor.
  • alkali metal hydroxide caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, and caustic soda is particularly preferable.
  • the amount of the alkali metal hydroxide used is 0.5 to 2 times the equivalent of the alcoholic hydroxyl group to be epoxidized in the epoxy compound represented by the general formula (6) or (7a) or (7b). It is preferable to make it equivalent.
  • the reaction temperature between the alcoholic hydroxyl group and the epihalohydrin in the epoxy compound represented by the general formula (6) or (7a) or (7b) is 20 ° C. or higher, preferably 30 ° C. or higher, 100 ° C.
  • the following ranges are preferred. The reason for this is that if the reaction temperature is lower than 20 ° C, the reaction rate becomes slower and the time required for the reaction becomes longer, while if the reaction temperature exceeds 100 ° C, many side reactions occur, which is not preferable. .
  • the reaction between the alcoholic hydroxyl group and the ephalohydrin in the epoxy compound represented by the general formula (6) or (7a) or (7b) is carried out by a quaternary basic salt such as dimethyl sulfoxide or a quaternary ammonium salt. It can also be carried out by adjusting the amount of the alkali metal hydroxide in the presence of a compound or 1,3-dimethyl-2-imidazoline and an alkali metal hydroxide.
  • alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, and cyclic ether compounds such as tetrahydrofuran are used as solvents. You may use together.
  • quaternary basic salt compounds that can be used include, for example, Nummonium mouthride, tetrabutylammonium bromide, trimethylpennylammonium halide, tetramethylammonium bicarbonate, tetramethylammonium benzoate, tetramethylammonium benzoate Oxide oxide at the mouth, tetraethylammonium hydroxide oxide at the mouth, tetramethylphosphonimide hydroxide, and the like.
  • the above catalysts can be used alone or in combination of two or more.
  • the amount used is the hydroxyl group of the epoxy compound represented by the general formula (6) or (7a) or (7b).
  • the range of 0.001 to 2 equivalents to 1 equivalent is preferable. More preferably 0.
  • the range is from 0.5 to 0.2 equivalents. If the amount is less than 0.001 equivalent, the effect is hardly exhibited, and the glycidyl ether group of the epoxy compound used as a raw material reacts with the hydroxyl group of the epoxy compound to increase the molecular weight, which is not preferable. On the other hand, even if the amount exceeds 2 equivalents, no further improvement in the effect is seen.
  • the polynuclear epoxy compound of the present invention thus obtained has a number average molecular weight of 400 to 5,000, preferably 500 to 300,000, more preferably 500 to 200,000.
  • the number average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is not sufficient.
  • it is more than 500 the solubility in a solvent is lowered, which is not preferable.
  • the epoxidation ratio can be appropriately selected depending on the purpose (depending on desired physical properties), but is preferably from 10 to L 0%, preferably from 30 to 90%, more preferably from 40 to 90%. 80%.
  • the polynuclear epoxy compound of the present invention is used alone or in combination with another epoxy resin, and can be cured by adding a curing agent and, if necessary, a curing accelerator or the like, as in the case of a normal epoxy resin. .
  • epoxy resin various known epoxy resins (D) as exemplified later can be used alone or in combination of two or more.
  • curing agent used examples include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds.
  • a specific example is Jamino Polyamide resin synthesized from diamine of diphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride To acid anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrofluoric anhydride, methyltetrahydrofluoric anhydride, methylnadic anhydride, hexahydrofluoric anhydride, methyl Examples thereof include xahydrofluoric anhydride, phenol novolak, and modified products thereof, imidazole, BF 3 -amine complex, and guanidine derivative. These curing agents may be used alone or in combination of two or more.
  • curing accelerator examples include imidazoles, tertiary amines, phenols, and metal compounds.
  • the epoxy resin composition containing the polynuclear epoxy compound of the present invention, the curing agent, and if necessary, the curing accelerator, etc. can be easily prepared under the same conditions as conventionally known methods. Cured product.
  • the polynuclear epoxy compound of the present invention, a curing agent, a filler, and other additives are mixed, and if necessary, sufficiently kneaded using an extruder, a kneader, a roll, or the like, until the epoxy resin is mixed.
  • the composition is obtained and the epoxy resin composition is melted, molded using a casting machine or a transfer molding machine, and then further heated to 80 to 200 ° C. to obtain a cured product. it can.
  • a prepreg obtained by dissolving the epoxy resin composition in a solvent, impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating is subjected to hot press molding. To obtain a cured product.
  • various additives such as an inorganic filler and an organic filler can be added as needed.
  • the epoxy resin composition containing the polynuclear epoxy compound of the present invention, the curing agent, and, if necessary, the curing accelerator and the like can be dissolved in a solvent to adjust the viscosity to a suitable one for the coating method.
  • Such solvents include, for example, methyl ethyl ketone, cyclohexano Ketones such as toluene; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl sorb, butyl sorb, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycoyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc .; ethyl acetate, butyl acetate, cellosolve acetate, butylacetosolve acetate, carbitol acetate Acetates such as butylcarbyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; ethanol, propanol
  • linear polynuclear epoxy compounds as described above in particular, a biphenyl skeleton and a naphthalene skeleton having a high softening point, or a bisphenol skeleton and a naphthylene skeleton were alternately copolymerized.
  • a polynuclear epoxy acrylate represented by the following general formula (2a) or (2b) obtained by reacting an unsaturated copolymer-containing monocarboxylic acid (c) with an alternating copolymer type linear polynuclear epoxy compound. It has been found that the compound (b) is capable of both photo-curing and thermo-curing, and that such a curing treatment gives a cured product having both excellent heat resistance and toughness.
  • X and Y represent different aromatic rings
  • X is at least one selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether. Both represent the aromatic ring residue of an aromatic epoxy compound having two glycidyl groups in one molecule, and ⁇ indicates dihydroxynaphthylene and its derivative.
  • At least two phenolic hydroxyl groups in one selected molecule At least two phenolic hydroxyl groups in one selected molecule
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an unsaturated monocarboxylic acid residue
  • the polynuclear epoxy acrylate compound (b) of the present invention regularly repeats different types of aromatic compounds as represented by the general formula (2a) or (2b).
  • a cured product with high mechanical strength is obtained, and a linear structure is used, and a polycarboxylic epoxy compound is reacted with an unsaturated group-containing monocarboxylic acid, so that photocuring or heat curing is performed.
  • a cured product having high heat resistance can be obtained, and a cured product having excellent adhesion to a substrate, water resistance, chemical resistance, electrical insulation, and moldability can be obtained.
  • More specific preferred embodiments are polynuclear epoxy acrylate compounds represented by the following general formulas (9a) to (9d).
  • R 3 to R 12 , Z and n have the same meaning as described above.
  • R 6 is all hydrogen atoms, or R 3 -R
  • R 6 are all methyl groups
  • R 7 to R 1 D are all hydrogen atoms
  • R 11 and R 12 are
  • ⁇ R 6 are all methyl groups, and the divalent naph ⁇ H
  • the polynuclear epoxy acrylate compound (b) represented by the general formula (2a) or (2b) is obtained by adding an unsaturated group-containing monocarboxylic acid (c) to the polynuclear epoxy compound represented by the following general formula (10). ) In the presence or absence of the aforementioned organic solvent, in the presence of a polymerization inhibitor or a reaction catalyst.
  • X, Y and n have the same meaning as described above, and Z 1 is independently of each other a hydrogen atom or a group represented by the general formula (4).
  • an unsaturated polynuclear epoxy acrylate compound (b) by reacting an unsaturated group-containing monocarboxylic acid (c) with the polynuclear epoxy compound represented by the general formula (10),
  • an unsaturated group-containing monocarboxylic acid is compounded in a ratio of 0.8 to 1.3 mol per 1 mol of the epoxy group contained in the compound, and is mixed with an inert solvent or without a solvent in about 60 to 15 mol. 0 ° C., preferably 70 ° C .: Heat to L 30 ° C., and carry out the reaction, preferably in the presence of air.
  • esterification catalyst examples include tertiary amines such as N, N-dimethylaniline, pyridine, and triethylamine, and hydrochlorides and bromates thereof; tetramethylammonium chloride, and tribenzylbenzyl ammonium chloride.
  • unsaturated group-containing monocarboxylic acid (c) include acrylic acid, methacrylic acid, hydroxyshethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth). Acrylate, trimethylolpropane (meta) acrylate, pen erythritol (meta) acrylate, dipentyl erythritol, pen (meta) acrylate, phenylglycidyl (Meth) acrylate, (meth) unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as acrylic acid cap lactone adducts.
  • acrylic acid and methacrylic acid are particularly preferred.
  • the number average molecular weight of the polynuclear epoxy acrylate compound (b) of the present invention is 40%. 0 to 100, 0000, preferably 500 to 7,000, more preferably 500 to 5,000. If the number average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is not sufficient. On the other hand, if it exceeds 100,000, the solubility in a solvent decreases, which is not preferable.
  • the polynuclear epoxy acrylate compound of the present invention can be used alone or in combination with other epoxy resins, by adding a curing agent and, if necessary, a curing accelerator, etc., as in the case of ordinary epoxy compounds. Can be cured.
  • epoxy resin various conventionally known epoxy resins (D) as exemplified later can be used alone or in combination of two or more. Further, as the hardening agent and the hardening accelerator, conventionally known various compounds as exemplified above can be used.
  • the polynuclear epoxy acrylate compound of the present invention may be used alone or in combination with another photosensitive (meth) acrylate compound to initiate photopolymerization in the same manner as in the case of a normal photosensitive (meth) acrylate compound.
  • the composition can be cured by irradiation with active energy rays.
  • photosensitive (meth) acrylate compounds and photopolymerization initiators various conventionally known photosensitive (meth) acrylate compounds (B) and photopolymerization initiators (C) may be used as exemplified later. Can be.
  • the above-mentioned polynuclear epoxy acrylate compound may be used alone or in combination with another photosensitive (meth) acrylate compound, by a heat polymerization method using an organic peroxide diazo compound or the like. It can be cured by a room temperature polymerization method using a peroxide and an accelerator.
  • Organic peroxides include t-butylperoxypentoxide, t-butylperoxy-12-ethylhexanoate, benzoyl peroxide, cyclohexanone peroxide, and methylethyl ketone peroxide. And bis-41-t-butylcyclohexylperoxydicarbonate. These can be used alone or in combination of two or more.
  • azo compound a known compound such as azobisisobutyltylonitrile alone or 2 More than one species can be used in combination.
  • Known accelerators include salts of polyvalent metals such as salts of octylic acid and naphthenic acid such as cobalt, iron and manganese, and organic amines such as dimethylaniline, getylaniline, p-toluidine and ethanolamine. They can be used alone or in combination of two or more.
  • the epoxy acrylate resin composition of the present invention in which the polynuclear epoxy acrylate compound, the photopolymerization initiator, the curing agent, and, if necessary, the curing accelerator, etc. are blended, is the same as the conventionally known method.
  • a cured product of the epoxy acrylate resin composition can be easily obtained by the above method.
  • the polynuclear epoxy acrylate compound of the present invention and a curing agent, a filler, and other additives may be sufficiently mixed, if necessary, with an extruder, a kneader, a mouth, etc. until uniform.
  • the epoxy acrylate resin composition After obtaining the epoxy acrylate resin composition, the epoxy acrylate resin composition is melted, molded using a casting or transfer molding machine, and further heated to 20 to 200 ° C. to obtain a cured product. Can be obtained. Further, the epoxy acrylate resin composition was dissolved in a solvent, impregnated into a base material such as glass fiber, nylon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and then heated and dried. The cured product can be obtained by subjecting the prepreg to hot press molding or irradiation with active energy rays.
  • a base material such as glass fiber, nylon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper
  • epoxy acrylate resin composition various additives such as an inorganic or organic filler can be mixed as necessary.
  • an epoxy acrylate resin composition containing the polynuclear epoxy acrylate compound of the present invention, a photopolymerization initiator, a curing agent, and, if necessary, a curing accelerator, etc. is dissolved in a solvent, and a viscosity suitable for a coating method is obtained. Can be adjusted.
  • a linear epoxy compound containing the above-mentioned heterogeneous aromatic rings regularly and repeatedly, particularly a biphenyl skeleton and a naphthalene skeleton having a high softening point, or a bisphenol skeleton and a naphthalene Epoxy obtained by reacting ephalohydrin in the presence of a solvent with the alcoholic hydroxyl group in the side chain in an alternating copolymerization type linear epoxy compound in which the skeleton is copolymerized alternately.
  • the compound is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting epoxy acrylate compound is reacted with a polybasic acid anhydride.
  • the resin composition containing such an active energy ray-curable resin as a photocurable component has heat resistance, adhesion, and non-resistance. It has been found that a cured product having excellent properties such as electrolytic plating property, electrical properties, flexibility, moisture absorption resistance and PC ⁇ (pre-shearing force) resistance is provided.
  • the active energy ray-curable resin (A) of the present invention is obtained by reacting a polynuclear epoxy compound (a ′) represented by the following general formula (5) with an unsaturated group-containing monocarboxylic acid (c), Photocurability and alkali developability obtained by reacting acrylate compound (b,) with polybasic acid anhydride (d), but containing different types of aromatic rings regularly and repeatedly
  • a cured product with high mechanical strength can be obtained, and a linear structure can provide a cured product with high heat resistance, as well as adhesion to substrates, electroless plating resistance, electrical properties, and flexibility.
  • a cured product excellent in moisture absorption resistance, PCT (pressure cook-force) resistance, etc. can be obtained.
  • X ′ and Y 5 represent different divalent aromatic rings,... Represents a glycidyl group and / or a hydrogen atom, and ⁇ represents an integer of 1 to 20.
  • the polynuclear epoxy compound (a 5 ) represented by the general formula (5) is a bifunctional aromatic compound.
  • known hydrin hydrin is used, aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene.
  • an alkali metal hydroxide such as caustic soda.
  • the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol are not limited to those exemplified above, but may be any of the bifunctional aromatic epoxy compounds exemplified above. Of course, it is preferable to use an epoxy compound and a bifunctional aromatic alcohol.
  • an unsaturated group-containing monocarboxylic acid is added to the polynuclear epoxy compound (a ′) represented by the general formula (5) in the presence or absence of an organic solvent, as described above, for example, in the presence of hydroquinone or oxygen.
  • Polymerization inhibitors such as triethylamine, quaternary ammonium salts such as triethylpentyl ammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine.
  • a reaction catalyst By reacting with C, a polynuclear epoxy acrylate compound (b 5 ) is obtained.
  • the activated energy linear curable resin (A) of the present invention is obtained by reacting a polybasic acid anhydride (d) with the alcoholic hydroxyl group of the epoxy acrylate compound (b,) produced by the above reaction.
  • a suitable amount of the polybasic acid anhydride (d) is a ratio of the anhydride group to the alcoholic hydroxyl group in the above reaction product of 99: 1 to 1:99. It is desirable to have an acid number in the range of 50-200 mg KOH / g, preferably 50-120 mg KOH / g.
  • the acid value of the active energy ray-curable resin (A) is lower than 50 mg KOH / g, the solubility in an alkaline aqueous solution becomes poor, and the development of the formed coating film becomes difficult.
  • it is higher than 200 mgKOH / g, the surface of the exposed portion is developed irrespective of the exposure conditions, which is not preferable.
  • the reaction is carried out in the presence or absence of the above-mentioned organic solvent and in the presence of a polymerization inhibitor such as hydroquinone-oxygen, usually at about 50 to 130 ° C.
  • a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazol, and triphenyl.
  • a phosphorus compound such as phosphine may be added as a catalyst.
  • Examples of the above polybasic acid anhydrides (d) include methyltetrahydrofluoric anhydride, tetrahydrofluoric anhydride, hexahydrofluoric anhydride, methylhexahydrofuran anhydride, and anhydrous anhydride.
  • the number average molecular weight of the active energy ray-curable resin (A) of the present invention is 400 to 100,000, preferably 500 to 7,000, more preferably 500 to 3, 0 0 0.
  • the number average molecular weight of the active energy ray-curable resin is less than 400, the toughness of the obtained cured product is not sufficient.
  • it exceeds 100,000 the solubility in a solvent is reduced, so that it is preferable. Absent.
  • the photo-curable and thermo-curable resin composition of the present invention which is capable of being fully developed, comprises a photosensitive (meth) acrylate compound (B) in addition to the active energy ray-curable resin (A).
  • a photosensitive (meth) acrylate compound (B) in addition to the active energy ray-curable resin (A).
  • the purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the composition.
  • Photosensitive (meth) acrylate compounds that are liquid at room temperature are used to increase the photoreactivity of the composition, adjust the composition to a viscosity suitable for various coating methods, and dissolve it in aqueous solutions.
  • the amount of the photosensitive (meth) acrylate compound (B) is 10 to 60 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin (A) (the same hereinafter as solid content), Preferably, the proportion is 15 to 50 parts by mass.
  • Examples of the photosensitive (meth) acrylate compound (B) include 2-hydroxyhexyl acrylate, 2-hydroxypropyl acrylate, pen erythritol triacrylate, and diphenyl erythritol triacrylate.
  • Water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentyl erythritol hexaacrylate, and the like.
  • Polyfunctional polyester acrylates of polyfunctional alcohols Trimethyl lip-to-mouth buns, polyfunctional alcohols such as hydrogenated bisphenol A or polyfunctional phenols such as bisphenol and biphenol Acrylates of ethylene oxide adducts and propylene oxide adducts of the above; polyfunctional or monofunctional polyurethane acrylates as isocyanate modified products of the above-mentioned hydroxyl group-containing acrylates; bisphenol A diglycidyl ether; hydrogenated Epoxy acrylates, which are (meth) acrylic acid adducts of bisphenol A diglycidyl ether or phenol novolak epoxy resin, and methacrylates corresponding to the above acrylates, may be used alone or in combination of two or more. The above can be used in combination. Among them, polyfunctional (meth) acrylate compounds having two or more (meth) acryloyloxy groups in one molecule Is preferred.
  • Examples of the photopolymerization initiator (C) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2, 2 — Acetophenones such as dimethoxy-2-phenylacetophenone, 2,2-ethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] —2-morpholinoaminopropanone 1,2-Benzyl-1-dimethylamino-1- (4-morpholinophenyl) 1-butane-11-one, aminoacetophenones such as N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethyl Luanthraquinone, 2-t-butylanthraquinone, 1-chloro Anthraquinones such as anth
  • photopolymerization initiators can be used alone or as a mixture of two or more thereof.
  • N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylamino Photoinitiating aids such as tertiary amines such as benzoate, triethylamine and triethanolamine can be added.
  • tertiary amines such as benzoate, triethylamine and triethanolamine
  • absorption in the visible light region Titanocene compounds such as CGI-784 (manufactured by Chipa and Specialty Chemicals) can also be added to promote the photoreaction.
  • photopolymerization initiators are 2-methyl-11- [4- (methylthio) phenyl] -12-morpholinoaminopropanone 1-1,2-benzyl-12-dimethylamino-1- (4-morpholinoff (Enyl) 1-butane-11-one, etc., but not particularly limited thereto.
  • they are not limited to the photopolymerization initiator and the photoinitiator, but can be used alone or in combination.
  • the amount of the photopolymerization initiator used (or the total amount thereof when a photoinitiator is used) is 0.1 to 25 mass% based on 100 parts by mass of the active energy ray-curable resin (A). Parts, preferably 0.5 to 20 parts by weight.
  • the amount of the photopolymerization initiator is less than the above range, the composition does not cure even when irradiated with active energy rays, or the irradiation time needs to be increased, so that it becomes difficult to obtain appropriate coating film properties.
  • the photopolymerization initiator is added in a larger amount than the above range, there is no change in photocurability, which is not economically preferable.
  • the photocurable and thermosetting composition of the present invention dissolves the active energy ray-curable resin (A) and the photosensitive (meth) acrylate compound (B).
  • the organic solvents as exemplified above can be used alone or in combination of two or more. The amount of the organic solvent can be set to any amount according to the application method.
  • polyfunctional epoxy compound (D) examples include Epikote 828, Epikoto 834, Epikote 101, Epikote 1004, manufactured by Japan Epoxy Resin Co., Ltd., and Dainippon Ink and Chemicals, Inc.
  • Epikoto 807 manufactured by Resin Co., Ltd. Epototo YD F—170, YD F—175, YD F—2004 manufactured by Toto Kasei Co., Ltd., manufactured by Ciba Specialty Chemicals Bisphenol F-type epoxy resin such as Araldide XPY306 (all trade names); EP-TOTO ST-2004, ST-200, ST-300 (manufactured by Toto Kasei Co., Ltd.) Nippon Epoxy Resin Co., Ltd.
  • Bisphenol A novolak type epoxy resin such as Epoxy® 15 S (trade name); Epoxy® YL-931, manufactured by Japan Epoxy Resin Co., Ltd., manufactured by Ciba's Specialty Chemicals Tetrafue two-roll ethane epoxy resin such as Araldide 163 (all trade names); Ciba Specialty's Araldide PT810 manufactured by Chemicals, TEPIC manufactured by Nissan Chemical Industry Co., Ltd.
  • the above-mentioned polyfunctional epoxy compound (D) improves properties such as adhesiveness and heat resistance of the solder resist by heat curing.
  • the compounding amount is sufficient in the range of 100 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable resin (A), and preferably 25 to 60 parts by mass. Percentage. If the amount of the polyfunctional epoxy compound (D) is less than 10 parts by mass, the PCT resistance tends to decrease due to the high hygroscopicity of the cured film, and the solder heat resistance and the electroless plating resistance are also low. Easy to be. On the other hand, if it exceeds 100 parts by mass, the imageability of the coating film and the electroless plating resistance of the cured film will be poor, and the PCT resistance will also be poor.
  • curing catalyst (E) examples include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenylimidazole.
  • Imidazole derivatives such as Louis Midazole, 1-Cyanoethyl — 2-phenylmidazole, 1-1 (2-Cyanoethyl) 1-2-ethyl-14-methylimidazole; Dicyandiamide, Benzyldimethylamine, 4- ( Amine compounds such as dimethylamino) 1 N, N-dimethylbenzylamine, 4-methoxy N, N-dimethylbenzylamine, 4-methyl-1-N, N-dimethylbenzylamine, adivic hydrazide, sebacic acid Examples of hydrazine compounds such as hydrazide; phosphorus compounds such as triphenylphosphine; 2MZ-A, 2MZ-OK, 2 ⁇ 4, 2 ⁇ 4 ⁇ , 2 24 ⁇ (both are trade names of imidazole compounds) manufactured by Kokusei Chemicals Co., Ltd.
  • the present invention is not limited to these, and any curing catalyst for an epoxy resin or any catalyst that promotes the reaction between an epoxy group and a carboxyl group may be used. I don't care.
  • guanamine, acetate guanamine, benzoguanamine, melamine, 2,4-diamino-1 6-methacryloyloxetyl-S-triazine, 2-vinyl-2,4-diamino-1 also function as an adhesion promoter.
  • S-triazine such as S-triazine, 2-vinyl-4,6-diamino-S-triazine 'isocyanuric acid adduct, 2,4-diaminol 6-methacryloyloxetyl-S-triazine and isocyanuric acid adduct
  • Derivatives can also be used, and preferably a compound that also functions as an adhesion promoter is used in combination with the curing catalyst.
  • the amount of the above-mentioned curing catalyst to be blended in a usual quantitative ratio is sufficient, for example, from 0.5 to 20 parts by mass, preferably from 0.5 to 100 parts by mass of the active energy ray-curable resin (A). :: 15.0 parts by mass.
  • the photocurable and thermosetting resin composition of the present invention may further include, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely powdered silicon oxide, amorphous silica, crystalline silica, and fused silica.
  • Known or customary inorganic fillers such as silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and myriki can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of a coating film and improving properties such as adhesion and hardness.
  • An appropriate amount of the inorganic filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass, per 100 parts by mass of the active energy linear curable resin (A).
  • composition of the present invention may further contain, if necessary, phthalocyanine blue, lid mouth cyanine 'green', aozin 'green, disazoeello, Chris Leo Violet, titanium oxide, carbon black, Nafurene Black, etc.
  • thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine; known and commonly used thickeners such as finely divided silica, organic pentonites, and montmorillonite
  • conventional additives such as silicone-based, fluorine-based, polymer-based antifoaming agents and z- or repelling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, etc.
  • the photo-curable and thermo-curable resin composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method. It is applied to the wiring board by screen printing, force coating, plate coating, roll coating, etc., for example, to evaporate the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. By drying, a tack-free coating film can be formed. Thereafter, the resist pattern is selectively exposed to active energy rays through a patterned photomask, and the unexposed portions are developed with a dilute aqueous solution to form a resist pattern.
  • a cured film (solder-resist film) with excellent properties and PCT (pressure resistance) is formed.
  • an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used.
  • a low-pressure mercury lamp a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate.
  • laser beams can be used as active energy rays.
  • methyl isobutyl ketone was distilled and recovered from the oil layer to obtain a polynuclear epoxy compound (a-2) having an epoxy equivalent of 376 g / eq.
  • a polynuclear epoxy compound (a-2) having an epoxy equivalent of 376 g / eq.
  • the obtained polynuclear epoxy compound (a-2) is calculated from the epoxy equivalent, about 1.05 of the 2.28 alcoholic hydroxyl groups in the general formula (7a) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 46%.
  • methylisobutyl ketone was recovered by distillation from the oil layer to obtain a polynuclear epoxy compound (a-3) having an epoxy equivalent of 458 gZeq.
  • a polynuclear epoxy compound (a-3) was calculated from the epoxy equivalent, about 1.32 of the 2.93 alcoholic hydroxyl groups in the general formula (7a) were epoxidized. I have. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 45%.
  • a polynuclear epoxy compound (a-5) having an epoxy equivalent of 309 g / eq. was obtained in the same manner as in Synthesis Example 4 except that the amount of 96% sodium hydroxide used was changed to 58 parts.
  • the obtained polynuclear epoxy compound (a-5) is calculated from the epoxy equivalent, about 0.50 of the 1.65 alcoholic hydroxyl groups in the general formula (7a) are epoxidized. . Therefore, the epoxidation rate of the alcoholic hydroxyl group is 30%.
  • the temperature in the reaction vessel was cooled to 40 ° C., and 190 parts of epichlorohydrin and 169 parts of toluene were added and dissolved, and then 70 parts of tetramethylammonium bromide was added. Was added, and the temperature was raised to 60 ° C. with stirring and maintained. Thereafter, 364 parts of a 48% aqueous sodium hydroxide solution were continuously dropped over 60 minutes. After the addition, the reaction was continued for another 6 hours.
  • the temperature in the reaction vessel was cooled to 40 ° C, 189 parts of epichlorohydrin and 1690 parts of toluene were added and dissolved, and 69 parts of tetramethylammonium bromide was added, followed by stirring.
  • the temperature was raised to and maintained at 60 ° C. Thereafter, 360 parts of a 48% aqueous sodium hydroxide solution was continuously dropped over 60 minutes. After the addition, the reaction was continued for another 6 hours. After completion of the reaction, the excess unreacted epichlorohydrin and most of the toluene were recovered by distillation under reduced pressure, and the reaction product containing the by-product salt and toluene was dissolved in methylisobutyl ketone and washed with water.
  • methylisobutyl ketone was distilled off from the organic solvent layer by distillation under reduced pressure to obtain a polynuclear epoxy compound (a-7) having an epoxy equivalent of 278 g / eq.
  • a-7 when calculated from the epoxy equivalent, about 1.56 out of 1.95 alcoholic hydroxyl groups in the epoxy compound (7) were epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is about 80%.
  • thermosetting resin composition is prepared by blending a curing accelerator (abbreviated as 2-phenyl-4,5-dihydromidazole, abbreviated as PDMI) and a solvent (carbitol acetate) and kneading with a 3-hole mill. I got things.
  • a curing accelerator abbreviated as 2-phenyl-4,5-dihydromidazole, abbreviated as PDMI
  • solvent carbbitol acetate
  • compositions of the above Examples and Comparative Examples were cured at 80 ° C. for 30 minutes and further at 180 ° C. for 1 hour, and the glass transition point, tensile strength, elongation, tensile modulus, Water absorption, electrical insulation, and pencil hardness were measured, and adhesion, acid resistance, and alkali resistance were evaluated.
  • compositions of the above Examples and Comparative Examples were applied by screen printing to a Tef board which had been washed and dried in advance, and dried at 80 ° C. for 40 minutes in a hot air circulation type drying oven. After cooling this to room temperature, it was exposed under the condition of an exposure amount of 500 mJ / cm 2 , and was cured in a hot air circulation type drying oven at 180 ° C. for 60 minutes. After cooling to room temperature, the cured coating film was peeled off from the Teflon plate to obtain an evaluation sample. The glass transition point of this evaluation sample was measured by the DMA method.
  • composition of each of the above Examples and Comparative Examples was applied to the entire surface of the comb-shaped electrode B-cup of IPCB-25 using Pachi-Koto Seie Co., Ltd.
  • the substrate was cured for 30 minutes at 180 ° C. for 1 hour to prepare an evaluation substrate.
  • a bias voltage of DC500 V was applied to this comb-shaped electrode, and the insulation resistance was measured.
  • the same evaluation substrate used for electrical insulation was immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C. for 30 minutes, taken out, and the state and adhesion of the coating film were comprehensively evaluated.
  • the criteria are as follows.
  • the coating film has blisters or swelling and falling off
  • test and evaluation were conducted in the same manner as the acid resistance test, except that the 10% by volume aqueous sulfuric acid solution was changed to a 10% by volume aqueous sodium hydroxide solution.
  • the cured product obtained from the polynuclear epoxy compound of the present invention has a high glass transition point, excellent mechanical strength, water absorption, adhesion, electrical insulation resistance, It has excellent properties such as hardness and chemical resistance.
  • the cured product obtained from the aromatic epoxy compound of the comparative example had a low glass transition point and was inferior in water absorption, hardness and the like.
  • methylisobutyl ketone was recovered by distillation from the oil layer to obtain a polynuclear epoxy compound (a-8) having an epoxy equivalent of 262 g // eq.
  • a polynuclear epoxy compound (a-8) was calculated from the epoxy equivalent, about 0.86 out of 1.57 alcoholic hydroxyl groups in the general formula (7a) were epoxidized. . Therefore, the epoxidation rate of alcoholic hydroxyl groups is 55%.
  • Synthesis example 1 2 277 parts of the polynuclear epoxy compound (a-6) obtained in Synthesis Example 6 was placed in a flask equipped with a stirrer, a condenser and a thermometer, and 233 parts of carbitol acetate was added, followed by heating and dissolution. Then, 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added, and the mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. .
  • this reaction solution is referred to as b-5 varnish.
  • Cresol novolak type epoxy resin (Epiclone N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 220 g / eq.) 5 27 parts of gas introduction pipe, stirrer, cooling pipe Then, the mixture was placed in a flask equipped with a thermometer, 300 parts of carbitol acetate was added, and the mixture was heated and dissolved, and 0.446 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. 95-105 of this mixture. C., and 173 parts of acrylic acid were gradually added dropwise, and the mixture was reacted for 16 hours.
  • this reaction solution is referred to as b′-1 varnish.
  • Cresol novolak type epoxy resin (Evicron N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 220 g / eq.) 600 parts of a gas introduction pipe, a stirrer, a cooling pipe and In a flask equipped with a thermometer, 300 parts of carbitol acetate was added, and the mixture was heated and dissolved, and 0.446 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C., and 98 parts of acrylic acid was gradually added dropwise to react for 16 hours. Less than, This reaction solution is referred to as b'-2 varnish.
  • a phenol novolak type epoxy resin (EPPN-201, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 190 g / eq.) 508 parts is equipped with a gas introduction pipe, a stirrer, a cooling pipe and a thermometer. Then, 300 parts of carbitol acetate was added, and the mixture was heated and dissolved, and 0.446 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105, and .192 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. Hereinafter referred to the reaction solution and the b 5 one 3 varnish.
  • DPHA Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
  • S-66 Silicone antifoam (Shin-Etsu Chemical Co., Ltd.)
  • R-974 Fine silica (Nippon Aerosil Co., Ltd.) The compositions of each of the above Examples and Comparative Examples were dried at 80 ° C. for 30 minutes, exposed at an exposure amount of 50 O m J / cm 2 , and cured, and further, Example 9 and Comparative Examples For 6, after exposure, cure at 150 ° C for 1 hour and measure glass transition point, tensile modulus, tensile strength, elongation, water absorption, pencil hardness, and electrical insulation resistance by the same method as above In addition, adhesion, acid resistance, and alkali resistance were evaluated. Table 4 shows the evaluation results. Table 4
  • the cured product obtained from the polynuclear epoxy acrylate compound of the present invention has a high glass transition point, excellent mechanical strength, water absorption, adhesion, and electric It has excellent properties such as insulation resistance, hardness and chemical resistance.
  • the cured product obtained from the aromatic epoxy acrylate compound of Comparative Example was inferior in glass transition point, water absorption, hardness and the like.
  • reaction solution is oxidized by potentiometric titration and total oxidation is measured, and the reaction is followed by the obtained addition rate.
  • the carboxyl group-containing active energy ray-curable resin thus obtained had an acid value of solid of 102 mgK ⁇ H / g.
  • this reaction solution is referred to as A-1 varnish.
  • the infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) and the nuclear magnetic field of the active energy linear curing resin (A-1) obtained in the present synthesis example were obtained.
  • reference material TMS (Te tetramethyl silane) ⁇ shows a thereto it FIGS. 5 and 6.
  • methyl isobutyl ketone was distilled and recovered from the oil layer to obtain a polynuclear epoxy compound (a-15) having an epoxy equivalent of 275 g / eq.
  • the resulting polynuclear epoxy compound (a-15) was When calculated from the siquivalent weight, about 0.82 of the 1.71 alcoholic hydroxyl groups in the general formula (7b) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 48%.
  • reaction solution is oxidized by potentiometric titration and total oxidation is measured.
  • the reaction is followed at the obtained addition rate, and the reaction rate is determined to be 95% or more.
  • the carboxyl group-containing active energy ray-curable resin thus obtained had a solid acid value of 1 O O mgK OH /.
  • this reaction solution is referred to as A-2 varnish.
  • reaction solution is oxidized by potentiometric titration and total oxidation is measured.
  • the reaction is followed at the obtained addition rate, and the reaction rate is determined to be 95% or more.
  • the thus obtained carboxyl group-containing active energy ray-curable resin had a solid acid value of 98 mgKOH / g.
  • this reaction solution is referred to as A-3 varnish.
  • the reaction product obtained in Synthesis Example 12 was cooled to 80 to 90 ° C., and 130 parts of tetrahydrophthalic anhydride was added, followed by a reaction for 8 hours.
  • the reaction is oxidized by potentiometric titration and the total oxidation is measured.
  • the reaction is followed by the obtained addition rate, and the reaction rate is determined to be 95% or more as the end point.
  • the carboxyl group-containing active energy ray-curable resin thus obtained had a nonvolatile content of 67% and an acid value of a solid of 102 mgKOHZg.
  • this reaction solution is referred to as A-4 varnish.
  • the reaction product obtained in Synthesis Example 13 was cooled to 80 to 90 ° C., and 130 parts of tetrahydrofuroic anhydride was added and reacted for 8 hours.
  • the reaction is oxidized by potentiometric titration and the total oxidation is measured.
  • the reaction is followed by the obtained addition rate, and the reaction rate is determined to be 95% or more.
  • the carboxyl group-containing active energy ray-curable resin thus obtained has a nonvolatile content of 67% and a solid acid value of 103 m. gKOH / g.
  • this reaction solution is referred to as A-5 varnish.
  • Cresol novolak type epoxy resin (Epiclone N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 220 g / eq.) 330 parts of gas injection pipe, stirrer, cooling The mixture was placed in a flask equipped with a tube and a thermometer, 400 parts of carbitol acetate was added, and the mixture was dissolved by heating. 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C, and acrylic acid (108 parts) was gradually added dropwise, and the mixture was reacted for 16 hours.
  • the reaction product was cooled to 80 to 90 ° C., added with 163 parts of tetrahydrofuric anhydride, and reacted for 8 hours.
  • the reaction solution is oxidized by potentiometric titration and the total oxidation is measured.
  • the reaction is followed by the obtained addition rate, and the reaction rate is 95% or more as the end point.
  • the carboxyl group-containing photosensitive resin thus obtained had a solid matter having an acid value of 100 mg K 0 HZ.
  • this reaction solution is referred to as B-1 varnish.
  • a phenol novolak type epoxy resin (EPPN-201, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 190 g / eq.) 32 2 parts of a gas introduction pipe, a stirrer, a cooling pipe and temperature In a flask equipped with a meter, 400 parts of carbitol acetate was added, and the mixture was dissolved by heating. 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C., and 122 parts of acrylic acid was gradually added dropwise and reacted for 16 hours.
  • EPPN-201 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 190 g / eq.
  • reaction product was cooled to 80 to 90 ° C., and 156 parts of phthalic anhydride with tetrahydric acid was added, and the mixture was reacted for 8 hours.
  • reaction solution is oxidized by potentiometric titration and the total oxidation is measured.
  • the reaction is followed by the obtained addition rate, and the reaction rate is determined to be 95% or more as the end point.
  • the carboxyl group-containing photosensitive resin thus obtained had a solid acid value of 96 mgK ⁇ H /.
  • this reaction solution is referred to as B-2 varnish.
  • the polynuclear epoxy compound (h) 352 parts obtained in Comparative Synthesis Example 4 was stirred with a stirrer, Put into a flask equipped with a condenser and a thermometer, add 400 parts of carbitol acetate, heat and dissolve, add 0.46 parts of methylhydroquinone and 1.38 parts of triphenyl phosphine, and add 95 to 105 parts.
  • the mixture was heated to C, and 75 parts of acrylic acid was gradually added dropwise and reacted for 16 hours.
  • the reaction product was cooled to 80 to 90 ° C., and 172 parts of tetrahydrofuroic anhydride was added and reacted for 8 hours.
  • reaction solution is oxidized by potentiometric titration and the total oxidation is measured, and the reaction is followed by the obtained addition rate.
  • the carboxyl group-containing photosensitive resin thus obtained had a solid acid value of 106 mgKOHZg.
  • this reaction solution is referred to as B-3 varnish.
  • composition of each of the above Examples and Comparative Examples was applied on the entire surface of the patterned copper foil substrate by screen printing, dried at 80 ° C for 40 minutes, 50 minutes, 60 minutes, or 70 minutes, and allowed to reach room temperature. after cooling, subjected to 60 seconds development of l% Na 2 C0 3 aqueous solution 30 ° C under the conditions of a spray pressure 2 kg / cm 2, to confirm the development remaining the presence of dried coating visually.
  • the evaluation criteria are as follows 9
  • compositions of the above Examples and Comparative Examples were applied by screen printing to a Tef board that had been washed and dried in advance, and dried at 80 ° C. for 40 minutes in a hot air circulation drying oven. After cooling to room temperature, exposure was performed under the conditions of an exposure amount of 50 OmJ / cm 2 , and curing was performed at 150 ° C. for 60 minutes in a hot-air circulation drying oven. After cooling to room temperature, the cured coating film was peeled off from the Teflon plate to obtain an evaluation sample. The glass transition point of this evaluation sample was measured by the DMA method.
  • compositions of the above Examples and Comparative Examples were applied to a glass plate whose mass was measured in advance by a screen printing method, and dried at 80 ° C. for 40 minutes in a hot air circulating drying oven. After cooling to room temperature, exposure was performed under the conditions of an exposure amount of 500 mJ / cm 2 , and curing was performed in a hot-air circulating drying oven at 150 ° C for 60 minutes to obtain an evaluation sample. After cooling to room temperature, the mass of the evaluation sample was measured. Next, this evaluation sample was treated using a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD) at 121 ° C, 100% RH for 24 hours, and the mass of the cured product after the treatment was measured. The water absorption of the cured product was determined.
  • a PCT device TABAI ESPEC HAST SYSTEM TPC-412MD
  • W1 is the mass of the evaluation sample
  • W2 is the mass of the evaluation sample after the PCT treatment
  • Wg is the mass of the glass plate.
  • ⁇ Adhesion> Determined visually according to JISD0202. The criteria are as follows.
  • composition of each of the above Examples and Comparative Example was applied to the entire surface of the comb-type electrode B coupon of IPCB-25 using a roll iron manufactured by Pilot Seie Co., Ltd. Dried at 0 ° C for 40 minutes. This was cooled to room temperature, exposed with exposure light amount 5 0 O mJZc m 2 condition, the curing in a hot air circulating drying oven performs for 60 minutes at 1 5 0 ° C, to obtain an evaluation sample. A bias voltage of DC500 V was applied to this comb-shaped electrode, and the insulation resistance was measured.
  • the same evaluation substrate used for electrical insulation was immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C. for 30 minutes, taken out, and the state of the coating film and the adhesion were comprehensively evaluated.
  • the criteria are as follows.
  • the coating film has blisters or swelling and falling off
  • the test was carried out in the same manner as in the acid resistance test except that the 10% by volume aqueous sulfuric acid solution was changed to a 10% by volume aqueous sodium hydroxide solution.
  • compositions of the above Examples and Comparative Examples were applied to a printed wiring board by screen printing, and dried at 80 ° C. for 40 minutes in a hot-air circulation drying oven. After cooling to room temperature, exposure was performed under the conditions of an exposure amount of 50 Om J / cm 2 , and curing was performed in a hot-air circulating drying oven at 150 ° C. for 60 minutes to obtain an evaluation sample. After cooling to room temperature, it was treated with PCT equipment (TABAI ESPEC HAST SYSTEM TPC-412MD) at 121 ° C and 2 atm for 168 hours, and the state of the cured film was evaluated. The judgment criteria are as follows.
  • the cured product obtained from the photocurable and thermosetting resin composition of the present invention has a high glass transition point, excellent mechanical strength, water absorption, and adhesion. It has excellent properties such as heat resistance, electrical insulation resistance, hardness, resistance to ashamedy, and PCT resistance.
  • the cured product obtained from the aromatic epoxy acrylate compound of Comparative Example was inferior in glass transition point, water absorption, hardness, PCT resistance and the like.
  • the polynuclear epoxy compound of the present invention is heat-curable, and the polynuclear epoxy acrylate compound of the present invention is capable of both curing by irradiation with active energy rays and thermal curing, and these cured products have high levels.
  • the balance between heat resistance and toughness is excellent, and it has excellent adhesion to the base material, and is also excellent in water resistance, chemical resistance, electrical insulation, etc., so various resists, adhesives, casting agents, laminates It can be advantageously used for applications such as paints, sealants and the like, and can be suitably used as a starting material for the active energy ray-curable resin of the present invention.
  • the photocurable and thermosetting resin composition of the present invention containing the active energy ray-curable resin of the present invention as a photocurable component is excellent in photocurability, alkali developability and adhesion to a substrate.
  • cured products with excellent heat resistance, water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexibility, PCT resistance, etc. can be obtained. solder one registry and a plate, in be used very advantageously as an interlayer insulating layer or the like of the multilayer printed wiring board Gill 0

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Abstract

A linear polynuclear epoxy compound comprising regular repetitions of aromatic rings of different kinds, especially one having a high softening point which is an alternating copolymer in which a biphenyl or bisphenol skeleton and a naphthalene skeleton occur alternately. By reacting the polynuclear epoxy compound with a monocarboxylic acid having an unsaturated group, a linear polynuclear epoxy acrylate compound is obtained which is photocurable and thermosetting. Furthermore, by reacting the polynuclear epoxy acrylate compound with a polybasic acid anhydride, a resin is obtained which is curable with active energy rays and is soluble in aqueous alkali solutions. Also provided is an alkali-developable photocurable/thermosetting resin composition which comprises (A) the resin curable with active energy rays, (B) a photosensitive (meth)acrylate compound, (C) a photopolymerization initiator, and (D) a polyfunctional epoxy compound.

Description

明 細 書 多核ェポキシ化合物、 それから得られる活性エネルギ一線硬化性樹脂  Description Polynuclear epoxy compound, active energy linear curable resin obtained from it
及びこれを用いた光.硬化性 ·熱硬化性樹脂組成物 技術分'野  And light-curable and thermosetting resin compositions using the same
本発明は、 異種の芳香環を規則的に繰り返し含有する線状の新規な多核ェ ポキシ化合物及び該多核エポキシ化合物から誘導される多核エポキシァクリ レート化合物並びにそれらを含有する硬化性樹脂組成物に関する。  The present invention relates to a novel linear polynuclear epoxy compound containing different aromatic rings regularly and repeatedly, a polynuclear epoxy acrylate compound derived from the polynuclear epoxy compound, and a curable resin composition containing the same.
本発明はまた、 上記多核エポキシ化合物又は多核エポキシァクリレート化' 合物から誘導される線状かつアル力リ可溶性の新規な活性エネルギー線硬化 性樹脂に関する。  The present invention also relates to a novel, linearly soluble, active energy ray-curable resin derived from the above-mentioned polynuclear epoxy compound or polynuclear epoxy acrylate compound.
さらに本発明は、 上記活性エネルギー線硬化性樹脂を用いた液状のアル力 リ現像可能な光硬化性 ·熱硬化性樹脂組成物並びにそれを用いた硬化皮膜形 成技術に関する。 背景技術  Further, the present invention relates to a photo-curable and thermo-curable resin composition which can be developed in liquid form using the active energy ray-curable resin and a cured film forming technique using the same. Background art
ビスフエノール A型エポキシ樹脂に代表されるエポキシ樹脂は、 その優れ た密着性や耐熱性、 耐薬品性、 電気絶縁性を有することから、 従来から広く 接着剤や注型剤、 積層材、 塗料、 封止剤などの用途に使用されている。  Epoxy resins typified by bisphenol A-type epoxy resins have excellent adhesiveness, heat resistance, chemical resistance, and electrical insulation, and have been widely used for adhesives, casting agents, laminates, paints, Used for applications such as sealants.
このエポキシ樹脂に関し、最近では、電気産業や半導体産業の発展に伴い、 例えば耐熱性、 強靱性、 耐水性、 耐薬品性などの特性向上が要求され、 かか る特性を満足すべく種々の新規なエポキシ化合物が提案されている。  In recent years, with the development of the electric and semiconductor industries, improvements in properties such as heat resistance, toughness, water resistance, and chemical resistance have been required for this epoxy resin. Various epoxy compounds have been proposed.
例えば、 耐熱性の優れたエポキシ化合物として、 クレゾ一ルノポラック型 エポキシ樹脂、 フエノールノボラヅク型エポキシ樹脂などの多核エポキシ樹 脂が提案されている。 しかし、 これらのエポキシ樹脂は、 確かに耐熱性には 優れているものの、 硬化時の収縮が大きく、 伸びが少なく、 強靱性に欠ける ため、 熱衝撃によるクラックが発生し易いという欠点があった。 これに対し、 上記欠点を解消し得る方法として、 エポキシ樹脂にゴム成分 をプレン ドする方法 （特開昭 6 3 - 1 9 9 2 1 8号公報） 、 二種類のェポキ シ樹脂をプレンドする方法 （日本特許第 2 7 8 3 1 1 6号公報） 、 ビフエ二 ル骨格とビスフヱノール骨格との共重合エポキシ樹脂 （日本特許第 2 7 8 9 3 2 5号公報） などが提案されている。 For example, polynuclear epoxy resins such as cresol nopolak epoxy resin and phenol novolak epoxy resin have been proposed as epoxy compounds having excellent heat resistance. However, although these epoxy resins are certainly excellent in heat resistance, they have a disadvantage that they tend to crack easily due to thermal shock because of their large shrinkage upon curing, low elongation, and lack of toughness. On the other hand, as a method for solving the above-mentioned drawbacks, a method of blending a rubber component into an epoxy resin (Japanese Patent Application Laid-Open No. Sho 63-1991) and a method of blending two types of epoxy resins are disclosed. (Japanese Patent No. 27831116), and a copolymerized epoxy resin of a biphenyl skeleton and a bisphenol skeleton (Japanese Patent No. 2789325) have been proposed.
しかし、 これらの方法によっても、 依然として耐熱性と強靱性とを共に満 足し得るエポキシ化合物を提供できないというのが実情であった。  However, the fact is that even with these methods, an epoxy compound that can satisfy both heat resistance and toughness cannot be provided.
一方、 硬化性、 作業性など成形性の優れた樹脂として、 ビスフヱノ一ル型 エポキシ樹脂ゃノボラック型エポキシ樹脂などの多価フエノール型エポキシ 樹脂と （メタ） アクリル酸から誘導されたエポキシ （メタ） ァクリ レートあ るいは不飽和ポリエステルなどラジカル重合型の樹脂が知られており、通常、 これらの樹脂はスチレンなどのようなラジカル重合性架橋剤を配合し、 ビニ ルエステル樹脂あるいは不飽和ポリエステル樹脂として広く用いられてい る。 しかしながら、 これらの樹脂は高温下における熱安定性の点で必ずしも 満足なレベルに達しておらず、 また、 硬化時の収縮が大きく、 伸びが少なく、 強靱性に欠けるため、 熱衝撃によるクラックが発生し易いという欠点があつ た。  On the other hand, as resins with excellent moldability such as curability and workability, epoxy (meth) acrylates derived from polyhydric phenol-type epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy resins and (meth) acrylic acid Radical polymerization type resins such as acrylates or unsaturated polyesters are known.In general, these resins contain a radical polymerization crosslinker such as styrene and are widely used as vinyl ester resins or unsaturated polyester resins. It has been done. However, these resins do not always reach a satisfactory level in terms of thermal stability at high temperatures, and have large shrinkage during curing, low elongation, and lack in toughness. There was a drawback that it was easy to do.
これに対し、 上記欠点を解消し得る方法として、 変性芳香族ァミンと、 重 合性架橋剤と、 ァクリロイル基及び/又はメ夕ク リロイル基を有するブ夕ジ ェン一ァクリロニト リル共重合体からなる樹脂組成物 （日本特許第 2 5 3 9 8 7 3号公報） 、 変性芳香族ポリアミン及び/又は変性芳香族ジァミンと、 エポキシ化合物と、 ラジカル重合性架橋剤からなる樹脂組成物 （特開平 1一 2 9 7 4 2 3号公報） などが提案されている。 しかし、 これらの方法も、 耐 熱性と強靱性とを共に満足させるまでにはまだまだ不充分である。  On the other hand, as a method for solving the above-mentioned disadvantages, a modified aromatic amine, a polymerizable cross-linking agent, and a bus phenyl acrylonitrile copolymer having an acryloyl group and / or a methyl acryloyl group are used. A resin composition comprising a modified aromatic polyamine and / or a modified aromatic diamine, an epoxy compound, and a radical polymerizable crosslinking agent (Japanese Patent Application Laid-Open No. No. 2997442). However, these methods are still insufficient to satisfy both heat resistance and toughness.
さらに、 現在、 一部の民生用プリント配線板並びに殆どの産業用プリント 配線板のソルダ一レジス トには、 高精度、 高密度の観点から、 紫外線照射後、 現像することにより画像形成し、 熱及び光照射で仕上げ硬化 （本硬化） する 液状現像型ソルダ一レジス トが使用されている。また環境問題への配慮から、 現像液として希アル力リ水溶液を用いるアル力リ現像タイプの液状ソルダ一 レジス トが主流になっている。 このような希アル力リ水溶液を用いるアル力 リ現像タイプのソルダ一レジス トとしては、 例えば、 特閧昭 6 1 - 2 4 3 8 6 9号公報には、 ノポラック型エポキシ化合物と不飽和一塩基酸の反応生成 物に酸無水物を付加した感光性樹脂、 光重合開始剤、 希釈剤及びエポキシ化 合物からなるソルダーレジス ト組成物が、 また特開平 3— 2 5 3 0 9 3号公 報には、 ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無 水物を付加した感光性樹脂、 光重合開始剤、 希釈剤、 ビニルト リアジン又は ビニルトリアジンとジシアンジアミ ドの混合 及びメラミン樹脂からなるソ ルダーレジス ト組成物が開示されている。 Furthermore, at present, the solder resists of some commercial printed wiring boards and most industrial printed wiring boards have been developed from the viewpoint of high precision and high density by forming an image by irradiating ultraviolet rays and developing them. In addition, a liquid development type solder resist that performs final curing (final curing) by light irradiation is used. Also, due to environmental concerns, Liquid soldering resists of the developing type using a dilute aqueous solution as a developing solution are mainly used. For example, Japanese Patent Application Laid-Open Publication No. Sho 61-224439 discloses a novolak type epoxy compound and an unsaturated A solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a basic acid, a photopolymerization initiator, a diluent, and an epoxide compound is disclosed in Japanese Patent Application Laid-Open No. 3-253930. The publications include a photosensitive resin in which an acid anhydride is added to the reaction product of a novolak epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, a mixture of vinyltriazine or vinyltriazine and dicyandiamide, and A solder resist composition comprising a melamine resin is disclosed.
しかしながら、 このような感光性樹脂は、 光硬化性やアルカリ現像性には 優れているものの、 高温下における熱安定性の点で必ずしも満足なレベルに 達しているとは言い難く、 また、 硬化時に収縮を生じる傾向があり、 伸びが 少なく強靭性に欠けるため、 熱衝撃によるクラックが発生し易いという欠点 があった。  However, such a photosensitive resin is excellent in photocurability and alkali developability, but is not necessarily at a satisfactory level in terms of thermal stability at high temperatures. It has a disadvantage that it tends to shrink, has low elongation, and lacks toughness, so that cracks easily occur due to thermal shock.
また、 近年のエレク トロニクス機器の軽薄短小化に伴うプリント配線板の 高密度化に対応して、 ソルダ一レジストにも高性能化が要求されている。 さ らに最近では、 リードフ レームと封止樹脂を用いた Q F P (クヮ ヅ ド ' フラ ヅ トノ ヅク ' ノ ヅケージ） 、 S O P (スモール ' アウ トライ ン ' パッケージ） 等と呼ばれる I Cパッケージに代わって、 ソルダーレジス トを施したプリン ト配線板の片側にボール状のはんだ等の金属をエリア状に配し、 もう片側に I Cチヅプをワイヤ一ボンディングもしくはバンプ等で直接接続し、 封止樹 脂で封止した構造を有する I Cパッケージが登場し、 B G A (ボール ' グリ ヅ ド ' アレイ） 、 C S P (チップ 'スケール ·パヅケージ） 等の呼び名で呼 ばれている。 これらのパッケージは、 同一サイズの Q F P等のパッケージよ りも多ピンでさらに小型化が容易である。 また実装においても、 ボール状は んだのセルファライメント効果により低い不良率を実現し、 急速にその導入 が進められている。 しかしながら、 従来市販されているアル力リ現像型ソルダーレジストを施 したプリント配線板では、 パッケージの長期信頼性試験である P C T耐性が 劣り、 ソルダ一レジスト皮膜の剥離が生じていた。 また、 ソルダーレジス ト の吸湿により、 パッケージ実装時のリフロー中にパッケージ内部で吸湿した 水分が沸騰し、 パッケージ内部のソルダ一レジスト皮膜及びその周辺にクラ ックが生じる、 いわゆるポップコーン現象が問題視されていた。 このような 耐吸湿性や長期信頼性における不具合は、 上記実装技術の場合のみに限られ るものではなく、 一般のプリント配線板のソルダ一レジストゃ、 ビルドァッ プ基板等の多層配線板の層間絶縁層など、 他の用途の製品においても望まし くない。 Also, in response to the increasing density of printed wiring boards as electronic devices become lighter and thinner in recent years, higher performance is also required for solder resists. More recently, solder packages have been replaced by IC packages called lead-frame and encapsulating resin, such as QFP (quad 'flat-knock' package) and SOP (small 'outline' package). Ball-shaped solder or other metal is arranged in an area on one side of the printed printed wiring board, and an IC chip is directly connected to the other side by wire bonding or bumping, and sealed with a sealing resin. IC packages with such a structure have appeared, and are called by names such as BGA (ball 'grid' array) and CSP (chip 'scale package'). These packages have more pins and are easier to miniaturize than packages of the same size, such as QFP. In mounting, a low defect rate is realized by the self-alignment effect of the ball-shaped solder, and its introduction is being promoted rapidly. However, in the case of printed wiring boards that have been coated with a newly developed solder resist, the PCT resistance, which is a long-term reliability test of the package, was poor, and the solder-resist film was peeled off. In addition, the so-called popcorn phenomenon, which causes cracks in the solder-resist film inside the package and its surroundings due to the absorption of moisture inside the package during reflow during package mounting due to the moisture absorption of the solder resist, is regarded as a problem. I was Such defects in the moisture absorption resistance and long-term reliability are not limited to the above-described mounting technology, but may be applied to the multilayered wiring board such as a solder-resist of a general printed wiring board or a build-up board. It is also undesirable in products for other uses, such as layers.
本発明は、上記の様な実情に鑑みなされたものであり、 その一つの目的は、 バランスのとれた耐熱性と強靱性に加え、 基材に対する密着性、 耐水性、 耐 薬品性、 電気絶縁性等に優れ、 かつ良好な成形性を持つ多核エポキシ化合物 及びそれを含有する熱硬化性樹脂組成物を提供することにある。  The present invention has been made in view of the above circumstances, and one of its objects is to provide well-balanced heat resistance and toughness, as well as adhesion to a substrate, water resistance, chemical resistance, and electrical insulation. An object of the present invention is to provide a polynuclear epoxy compound having excellent moldability and good moldability, and a thermosetting resin composition containing the same.
本発明の他の目的は、 上記のような優れた特性を有する多核エポキシ化合 物から誘導され、 活性エネルギー線の照射による硬化及び熱硬化のいずれも 可能な多核エポキシァクリレート化合物及びそれを含有する硬化性樹脂組成 物を提供することにある。  Another object of the present invention is to provide a polynuclear epoxy acrylate compound derived from a polynuclear epoxy compound having the above-described excellent properties and capable of being cured by both irradiation with active energy rays and heat. It is an object of the present invention to provide a curable resin composition.
本発明の別の目的は、 高温下における熱安定性に優れ、 バランスのとれた 耐熱性と強靭性を有すると共に、 光硬化性やアル力リ現像性にも優れる活性 エネルギー線硬化性樹脂を提供することにある。  Another object of the present invention is to provide an active energy ray-curable resin which has excellent heat stability at high temperatures, has well-balanced heat resistance and toughness, and also has excellent photocurability and high reversibility developability. Is to do.
本発明のさらに別の目的は、 従来からのプリント配線板のソルダーレジス トゃ多層配線板の層間絶縁層などに要求される耐熱性、 密着性、 耐無電解め つき性、 電気特性、 フレキシブル性等の特性を維持もしくは向上させ、 かつ、 特に I Cパッケージに要求される耐吸湿性並びに P C T (プレッシャークッ カー）耐性等の特性に優れる硬化皮膜が得られ、 プリント配線板の高密度化、 面実装化に対応可能でアル力リ現像可能な液状の光硬化性 ·熱硬化性樹脂組 成物を提供することにある。 発明の開示 Still another object of the present invention is to provide a conventional solder resist for a printed wiring board and heat resistance, adhesion, electroless plating resistance, electrical characteristics, and flexibility required for an interlayer insulating layer of a multilayer wiring board. And other properties, and a cured film with excellent properties such as moisture absorption resistance and PCT (pressure cooker) resistance required especially for IC packages can be obtained. It is an object of the present invention to provide a liquid photocurable / thermosetting resin composition which can be developed and can be developed completely. Disclosure of the invention
前記目的を達成するために、本発明の第一の側面によれば、下記一般式（ 1 ) で表わされる多核エポキシ化合物 （a) 及びそれを含有する熱硬化性樹脂組 成物が提供される。  In order to achieve the above object, according to a first aspect of the present invention, there is provided a polynuclear epoxy compound (a) represented by the following general formula (1) and a thermosetting resin composition containing the same. .
0M  0M
CH2— CH— CH2— 0— X—0- -CH2— CH— CH2— 0-Y— CH 2 — CH— CH 2 — 0— X—0- -CH 2 — CH— CH 2 — 0-Y—
\ /  \ /
0  0
OM  OM
I  I
-0— CH2 -CH— CH2 -0— X— 0- -CH2一 CH— CH2 · · · (1) -0— CH 2 -CH— CH 2 -0— X— 0- -CH 2 CH— CH 2 · · · (1)
」ft \ /  "Ft \ /
0  0
式中、 Xと Yは異なる芳香璟を表わし、 Xはビフヱノール型ジグリシジル ェ一テル、 ビキシレノール型ジグリシジルェ一テル、 ビスフエノール型ジグ リシジルエーテル及びナフ夕レン型ジグリシジルエーテルよりなる群から選 ばれた少なく とも 1種の 1分子中に 2個のグリシジル基を有する芳香族ェポ キシ化合物の芳香環残基を表わし、 Υはジヒ ドロキシナフ夕レン及びその誘 導体、 ビフヱノール及びその誘導体、 ビキシレノール及びその誘導体、、ビス フエノール及びその誘導体、 及びハイ ドロキノン及ぴその誘導体よりなる群 から選ばれた少なく とも 1種の 1分子中に 2個のフエノール性水酸基を有す る芳香族アルコールの芳香璟残基を表わし、 Μはグリシジル基及び/又は水 素原子を表わし、 ηは 1~20の整数を表わす。  In the formula, X and Y represent different aromatic groups, and X is selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether. Represents the aromatic ring residue of an aromatic epoxy compound having at least two glycidyl groups in one molecule, and 、 represents dihydroxynaphthylene and its derivatives, biphenol and its derivatives, bixylenol and Aromatic residues of aromatic alcohols having at least two phenolic hydroxyl groups in one molecule selected from the group consisting of derivatives thereof, bisphenol and its derivatives, and hydroquinone and its derivatives Represents a glycidyl group and / or a hydrogen atom, and η represents an integer of 1 to 20.
上記のような本発明の多核エポキシ化合物は、 異種の芳香環を規則的に繰 り返し含有する線状多核エポキシ化合物、 特に軟化点の高いビフエ二ル骨格 とナフ夕レン骨格、 あるいはビスフエノール骨格とナフ夕レン骨格とが交互 に共重合された交互共重合型の線状多核エポキシ化合物であるため、 該多核 エポキシ化合物の硬化物は、高いレベルで耐熱性と強靱性のパランスがとれ、 S材に対する密着性に優れると共に、 耐水性、 耐薬品性、 電気絶縁性等に優 れ 本尧明の第二の側面によれば、 下記一般式 （ 2 a) 又は （ 2 b) で示され る多核エポキシァクリレート化合物 （b) 及びそれを含有する硬化性樹脂組 成物が提供される。 The polynuclear epoxy compound of the present invention as described above is a linear polynuclear epoxy compound containing different aromatic rings regularly and repeatedly, particularly a biphenyl skeleton and a naphthylene skeleton or a bisphenol skeleton having a high softening point. And a naphthylene skeleton are alternately copolymerized, so that the cured product of the polynuclear epoxy compound has a high level of heat resistance and toughness balance, and Excellent adhesion to materials and excellent water resistance, chemical resistance, electrical insulation, etc. According to a second aspect of the present invention, there is provided a polynuclear epoxy acrylate compound (b) represented by the following general formula (2a) or (2b) and a curable resin composition containing the same. Is done.
0Z 0Z
Z'一 0— X— 0- -CH2— CH— CH2— 0— Y— 0- Z 'one 0— X— 0- -CH 2 — CH— CH 2 — 0— Y— 0-
0Ζ 0Ζ
一 CH2 -CH-CH2— 0— X— 0- -Z' (2a) One CH 2 -CH-CH 2 — 0— X— 0- -Z '(2a)
n oz  n oz
CH2— CH— CH2— 0— X—〇- ■CH2— CH-CH2一 0— Y— 0— CH 2 — CH— CH 2 — 0— X—〇- ■ CH 2 — CH-CH 2 1 0— Y— 0—
\ /  \ /
〇  〇
oz  oz
CH2— CH— CH2— 0— X— 0- - CH2— CH— CHi (2b) n \ / CH 2 — CH— CH 2 — 0— X— 0--CH 2 — CH— CHi (2b) n \ /
0 式中、 X、 Y及び nは前記と同じ意味を有し、 Zは互いに無関係に、 下記 —般式 （3) もしくは （4) で示される基又は水素原子を表わし、 かつ Zの 少なくとも 1個は一般式 （ 3 )で示される基であり、 Z， は互いに無関係に、 下記一般式 （3， ) もしくは （4， ) で示される基を表わす。  In the formula, X, Y and n have the same meanings as described above, and Z independently of one another represents a group represented by the following general formula (3) or (4) or a hydrogen atom, and at least one of Z Is a group represented by the general formula (3), and Z, independently of each other, represents a group represented by the following general formula (3,) or (4,).
R1 0 R1 R 1 0 R 1
I II  I II
一 CH2 -C-CH2 -0-C-Rs (3) CH2一 C- ■CHi (4) One CH 2 -C-CH 2 -0- CR s (3) CH 2 one C- ■ CHi (4)
\  \
OH 〇  OH 〇
0  0
一 CH2 — CH— CH2 - 0 C一 R2 · ' (3' ) 一 CH: ■CH-CH: (4， ) One CH 2 - CH- CH 2 - 0 C one R 2 · '(3') one CH: ■ CH-CH: ( 4,)
\ /  \ /
OH 0 ·  OH 0
式中、 R1は水素原子又はメチル基を表わし、 R2は不飽和モノカルボン酸 残基を表わす。 In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an unsaturated monocarboxylic acid residue.
上記のような本発明の多核エポキシァクリレート化合物は、 活性エネルギ —線の照射による硬化および熱硬化のいずれも可能であり、 .その硬化物は高 いレベルで耐熱性と強靱性のパランスがとれ、 基材に対する密着性に癧れる と共に、 耐水性、 耐薬品性、 電気絶縁性等に優れている。 The polynuclear epoxy acrylate compound of the present invention as described above can be either cured by irradiation with active energy rays or thermally cured. It has a good balance of heat resistance and toughness at a low level, has poor adhesion to the substrate, and has excellent water resistance, chemical resistance, electrical insulation, etc.
本発明の第三の側面によれば、 下記一般式 （5) で示される多核エポキシ 化合物 （a， ) と不飽和基含有モノカルボン酸 （c) との反応生成物 （b， ) に多塩基酸無水物 （d) を反応させて得られる活性エネルギー線硬化性樹脂 が提供される。  According to a third aspect of the present invention, a reaction product (b,) of a polynuclear epoxy compound (a,) represented by the following general formula (5) and a monocarboxylic acid containing an unsaturated group (c) is polybasic: An active energy ray-curable resin obtained by reacting the acid anhydride (d) is provided.
0M  0M
I I
CH2— CH— CH: -0— X' — 0- — CH2— CH— CH2一〇一 Y' — 0— CH 2 — CH— CH : -0— X '— 0- — CH 2 — CH— CH 2 one-one Y' — 0—
\ /  \ /
0  0
0M  0M
■CH2— CH— CH2— 0-X' — 0- — CH2— CH-CH2 · · ' (5) ■ CH 2 — CH— CH 2 — 0-X '— 0- — CH 2 — CH-CH 2 ·' (5)
n \ /  n \ /
0  0
式中、 X3 と Y， は互いに異なる 2価の芳香環を表わし、 Μはグリシジル 基及び/又は水素原子を表わし、 ηは 1〜20の整数を表わす。 In the formula, X 3 and Y, represent different divalent aromatic rings, Μ represents a glycidyl group and / or a hydrogen atom, and η represents an integer of 1 to 20.
さらに本発明の第四の側面によれば、 （Α) 上記活性エネルギー線硬化性 樹脂、 （Β) 感光性 （メタ） ァクリレート化合物、 （C) 光重合開始剤、 及 び （D) —分子中に 2個以上のエポキシ基を有するエポキシ化合物 （以下、 多官能エポキシ化合物という） を含有する、 アルカリ水溶液により現像可能 な光硬化性 ·熱硬化性樹脂組成物が提供される。  Furthermore, according to the fourth aspect of the present invention, (Α) the active energy ray-curable resin, (Β) a photosensitive (meth) acrylate compound, (C) a photopolymerization initiator, and (D) The present invention provides a photo-curable / thermo-curable resin composition which can be developed with an aqueous alkali solution and contains an epoxy compound having two or more epoxy groups (hereinafter, referred to as a polyfunctional epoxy compound).
各成分の配合割合は特定の割合に限定されるものではないが、 （Α) 上記 活性エネルギー線硬化性樹脂 100質量部に対して、 （Β) 上記感光性 （メ 夕） メタァクリレート化合物を 10〜 60質量部、 好ましくは 1 5〜 50質 量部、 （C) 上記光重合開始剤を 0. 1〜 25質量部、 好ましくは 0. 5〜 20質量部、 （D) 上記多官能エポキシ化合物を 1 0〜100質量部、 さら に必要ならば （Ε) エポキシ硬化触媒を 0. 1〜 20質量部の割合で用いる ことが望ましい。  The mixing ratio of each component is not limited to a specific ratio, but (Α) 100 parts by mass of the active energy ray-curable resin, and (Β) the photosensitive (meth) methacrylate compound in 10 to 10 parts by mass. 60 parts by mass, preferably 15 to 50 parts by mass, (C) 0.1 to 25 parts by mass of the photopolymerization initiator, preferably 0.5 to 20 parts by mass, and (D) the polyfunctional epoxy compound. It is preferable to use the epoxy curing catalyst in a ratio of 0.1 to 20 parts by mass, more preferably 100 to 100 parts by mass, and if necessary (Ε).
本発明の活性エネルギー線硬化性樹脂は、 異種の芳香璟を規則的に繰り返 し含有する線状多核エポキシァクリレート化合物、 特に軟化点の高いビフエ ニル骨格とナフタレン骨格、 あるいはビスフエノール骨格とナフ夕レン骨格 とが交互に共重合された交互共重合型の線状多核エポキシァクリレート化合 物の多塩基酸無水物付加物であるため、 光硬化性、 アルカリ可溶性であると 共に、 高温下における熱安定性に優れ、 高いレベルでバランスのとれた耐熱 性と強靭性を有する。 また、 このような活性エネルギー線硬化性樹脂を光硬 化性成分とし" ^含有する本発明の光硬化性 ·熱硬化性樹脂組成物は、 光硬化 性、 アルカリ現像性ゃ基材に対する密着性に優れると共に、 耐熱性、 耐水性、 耐無電解めつき性、 耐薬品性、 電気絶縁性、 フレキシブル性、 P C T耐性等 に優れた硬化物が得られる.。 図面の簡単な説明 The active energy ray-curable resin of the present invention is a linear polynuclear epoxy acrylate compound containing a different kind of aromatic compound regularly and repetitively, particularly bife having a high softening point. Since it is a polybasic acid anhydride adduct of an alternating copolymerization type linear polynuclear epoxy acrylate compound in which a phenyl skeleton and a naphthalene skeleton, or a bisphenol skeleton and a naphthylene skeleton are alternately copolymerized. As well as being curable and alkali-soluble, it has excellent thermal stability at high temperatures, and has a high level of balanced heat resistance and toughness. In addition, the photocurable and thermosetting resin composition of the present invention containing such an active energy ray-curable resin as a photocurable component has a photocurable property, an alkali developable property and an adhesive property to a substrate. The cured product is excellent in heat resistance, water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexibility, PCT resistance, etc ..
図 1は、 合成例 2で得た多核エポキシ化合物 （a— 2 ) の赤外線吸収スぺ ク トルであり ；  FIG. 1 is an infrared absorption spectrum of the polynuclear epoxy compound (a-2) obtained in Synthesis Example 2;
図 2は、 合成例 2で得た多核エポキシ化合物 （a— 2 ) の核磁気共鳴スぺ ク トルであり ；  FIG. 2 is a nuclear magnetic resonance spectrum of the polynuclear epoxy compound (a-2) obtained in Synthesis Example 2;
図 3は、 合成例 8で得た多核エポキシァクリレート化合物 （b— 1 ) の赤 外線吸収スぺク トルであり ；  FIG. 3 is an infrared absorption spectrum of the polynuclear epoxy acrylate compound (b-1) obtained in Synthesis Example 8;
図 4は、 合成例 8で得た多核エポキシァクリレート化合物 （b— 1 ) の核 磁気共鳴スぺク トルであり ；  FIG. 4 is a nuclear magnetic resonance spectrum of the polynuclear epoxy acrylate compound (b-1) obtained in Synthesis Example 8;
図 5は、 合成例 1 4で得た活性エネルギー線硬化性樹脂 （A— 1 ) の赤外 線吸収スぺク トルであり ； そして  FIG. 5 is an infrared absorption spectrum of the active energy ray-curable resin (A-1) obtained in Synthesis Example 14;
図 6は、 合成例 1 4で得た活性エネルギ一線硬化性樹脂 （A— 1 ) の核磁 気共鳴スぺク トルである。 発明を実施するための最良の形態  FIG. 6 is a nuclear magnetic resonance spectrum of the active energy linear curable resin (A-1) obtained in Synthesis Example 14. BEST MODE FOR CARRYING OUT THE INVENTION
本発明者らは、 前記目的を達成するため鋭意検討を重ねた結果、 前記 X及 び Yで表わされる異種の芳香環を規則的に繰り返し含有する線状エポキシ化 合物、 特に軟化点の高いビフヱニル骨格とナフ夕レン骨格、 あるいはビスフ C The present inventors have conducted intensive studies to achieve the above object, and as a result, as a result, a linear epoxy compound containing regularly different kinds of aromatic rings represented by X and Y, particularly having a high softening point. Biphenyl skeleton and naphthylene skeleton or Bisphenyl C
\ H  \ H
ェノー 2 oル骨格とナフ夕レン骨格とが交互に共重合された交互共重合型の線状 エポキシ化 C Alternating copolymeric linear epoxidation in which the phenol 2 skeleton and the naphthylene skeleton are alternately copolymerized. Epoxidation C
H合物におけるアルコール性水酸基にェピハロヒ ドリンを反応させ て得られる多核 Cエポキシ化合物が、 優れた耐熱性と強靱性を併せ持つ硬化物  A polynuclear C-epoxy compound obtained by reacting an alcoholic hydroxyl group in an H compound with an epihalohydrin is a cured product that has both excellent heat resistance and toughness
H  H
を与えることを見出した。 Found to give.
すなわち、 本発明の多核エポキシ化合物 （ a ) は、 下記一般式 （ 1 ) で表 わされるように、 異種の芳香環を規則的に繰り返し含有するため機械的強度 の高い硬化物が得られ、 また線状構造としたことによって、 さらにェピハ口 ヒ ドリンとの反応により多核エポキシ化合物としたことによって、 耐熱性の 高い硬化物が得られると共に基材に対する密着性、 耐水性、 耐薬品性、 電気 絶縁性、 成形性等に優れた硬化物が得られるものである。  That is, the polynuclear epoxy compound (a) of the present invention, as represented by the following general formula (1), contains a different type of aromatic ring regularly and repeatedly, so that a cured product having high mechanical strength can be obtained. In addition, by using a linear structure, and by forming a polynuclear epoxy compound by reacting with hydrin at the end of epipah, a cured product with high heat resistance can be obtained, as well as adhesion to substrates, water resistance, chemical resistance, and electricity. A cured product having excellent insulation properties and moldability can be obtained.
0M  0M
-o—x _o- -C H2— C H— C H2一 0— Y- -o—x _o- -CH 2 — CH— CH 2 1 0— Y-
0 M 0 M
•0— C H2— C H— CH 2— 0— X— 0- -C H2— C H-CH: ( 1 )• 0— CH 2 — CH— CH 2 — 0— X— 0- -CH 2 — C H-CH : (1)
」 n \ / "N \ /
0  0
式中、 Xと Yは異なる芳香環を表わし、 Xはビフエノール型ジグリシジル エーテル、 ビキシレノール型ジグリシジルエーテル、 ビスフエノール型ジグ リシジルエーテル及びナフ夕レン型ジグリシジルェ一テルよりなる群から選 ばれた少なく とも 1種の 1分子中に 2個のグリシジル基を有する芳香族ェポ キシ化合物の芳香環残基を表わし、 Υはジヒ ドロキシナフ夕レン及びその誘 導体、 ビフエノ一ル及びその誘導体、 ビキシレノール及びその誘導体、 ビス フヱノール及びその誘導体、 及びハイ ドロキノン及びその誘導体よりなる群 から選ばれた少なく とも 1種の 1分子中に 2個のフエノール性水酸基を有す る芳香族アルコールの芳香璟残基を表わし、 Μはグリシジル基及び/又は水 素原子を表わし、 ηは 1〜2 0の整数を表わす。  In the formula, X and Y represent different aromatic rings, and X is at least one selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether. Each represents an aromatic ring residue of an aromatic epoxide compound having two glycidyl groups in one molecule, and Υ represents dihydroxynaphthylene and its derivative, biphenyl and its derivative, bixylenol and The aromatic residue of an aromatic alcohol having at least two phenolic hydroxyl groups in one molecule selected from the group consisting of its derivatives, bisphenol and its derivatives, and hydroquinone and its derivatives Represents a glycidyl group and / or a hydrogen atom, and η represents an integer of 1 to 20.
上記多核エポキシ化合物は、 種々の方法により製造できるが、 特に下記一 般式 （ 6 ) で表わされるエポキシ化合物のアルコール性水酸基とェピハロヒ C The above-mentioned polynuclear epoxy compound can be produced by various methods. In particular, the alcoholic hydroxyl group of the epoxy compound represented by the following general formula (6) and the ephalophenol C
ドリン 2 oとを反応させて得られる多核エポキシ化合物が好ましく、 また比較的 容易に製造 C Polynuclear epoxy compounds obtained by reacting with drin 2 o are preferred, and are relatively easy to produce.
Hできる。  H can.
0H  0H
-CH: -0— X—〇- -CH2一 CH— CH2— 0— Y—0- -CH: -0— X—〇- -CH 2 One CH— CH 2 — 0— Y—0-
OH OH
-CH2— CH— CH2— 0— X— 0 (6)-CH 2 — CH— CH 2 — 0— X— 0 (6)
Figure imgf000012_0001
式中、 X、 Y、 及び ηは前記と同じ意味を有する。
Figure imgf000012_0001
In the formula, X, Y, and η have the same meaning as described above.
より具体的な好適な態様は、 下記一般式 （ 7 a) 又は （ 7 b) で表わされ るエポキシ化合物のアルコール性水酸基とェピハロヒ ドリンとを反応させて 得られる下記一般式 （ 8 a) 又は （ 8 b) で表わさ oれる多核エポキシ化合物 である。  A more specific preferred embodiment is the following general formula (8a) or (8a) obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (7a) or (7b) with ephalohydrin It is a polynuclear epoxy compound represented by (8b).
Figure imgf000012_0002
11
Figure imgf000012_0002
11
Figure imgf000013_0001
Figure imgf000013_0001
OM  OM
-CH2— CH— CH (8b) n c -CH 2 — CH— CH (8b) nc
\ H  \ H
式中、 R3、 R4、 5, ： R 6は同一の又は互いに異なる、一 o水素原子又は炭 In the formula, R 3 , R 4 , 5 , R 6 are the same or different, are each a hydrogen atom or carbon
/ c  / c
素数 1〜4のアルキル基を表わし、 R7、 R8、 R9、 R1 Qは同 H一の又は互い に異なる、水素原子、炭素数 1〜 4のアルキル基又はハロゲン原子を表わし、 R 1 xs H 12は同一の又は互いに異なる、 水素原子、 メチル基又はハロゲン 化メチル基を表わし、 Mはグリシジル基及び/又は水素原子を表わし、 nは 1〜 20の整数を表わす。 R 7 , R 8 , R 9 , and R 1 Q represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, which are the same or different from each other; 1 x s H 12 varies same or each a hydrogen atom, a methyl group or a halogenated methyl group, M represents a glycidyl group and / or a hydrogen atom, n represents an integer of 1-20.
好適な態様においては、 上記一般式 （7 a)、 （7 b)、 （8 a) 及び （8 b)で表わされるエポキシ化合物において、 R3〜： R 6が全て水素原子である か又は R3〜RSが全てメチル基であり、 また： R7〜： R10が全て水素原子、 R 1 1及び R12が全てメチル基であり、 一方、 二価のナフ夕レン環残基が 1 , 5—、 1 , 6—、 2, 6—又は 2 , 7—置換体である。 特に好適な態様にお いては、 前記 R3〜R6は全てメチル基であり、 かつ前記二価のナフタレン環 残基は 1， 5—、 1 , 6—又は 2 , 6—置換体である。 In a preferred embodiment, in the epoxy compound represented by the general formulas (7a), (7b), (8a) and (8b), R 3 to R 6 are all hydrogen atoms or R 6 3 to R S are all methyl groups, and: R 7 to R 10 are all hydrogen atoms, R 11 and R 12 are all methyl groups, while divalent naphthylene ring residue is 1 , 5—, 1, 6—, 2, 6— or 2,7—substituted. In a particularly preferred embodiment, R 3 to R 6 are all methyl groups, and the divalent naphthalene ring residue is a 1,5-, 1,6- or 2,6-substituted product .
なお、 前記一般式 （6) で表わされるエポキシ化合物の数平均分子量の増 大に伴いェピハ口ヒドリンによるエポキシ化の収率が低下するが、 この点に ついても本発明では、 触媒としてのアル力リ金属水酸化物の量を調節するこ とにより、 アルコール性水酸基を所望の割合にてエポキシ化することができ る。 Incidentally, the yield of epoxidation by hydrin hydrin decreases as the number average molecular weight of the epoxy compound represented by the general formula (6) increases. Further, in the present invention, the alcoholic hydroxyl groups can be epoxidized at a desired ratio by adjusting the amount of the metal hydroxide as a catalyst.
以下、 本発明の多核エポキシ化合物について詳細に説明する。  Hereinafter, the polynuclear epoxy compound of the present invention will be described in detail.
まず、 前記一般式 （ 6 ) 又は （ 7 a ) 、 ( 7 b ) で表わされるエポキシ化 合物について説明する。  First, the epoxy compound represented by the general formula (6) or (7a) or (7b) will be described.
前記一般式 （ 6 ) で表わされるエポキシ化合物は、 1分子中に 2個のグリ シジル墓を有する芳香族エポキシ化合物 （以下、 二官能芳香族エポキシ化合 物という） と、 1分子中に 2個のフヱノール性水酸基を有する芳香族アルコ —ル （以下、 二官能芳香族アルコールという） とを原料として、 後述するよ うな公知のェ一テル化触媒を用い、 溶媒中又は無溶媒下、 交互に重合させる 方法によって容易に製造するこ ができる。  The epoxy compound represented by the general formula (6) includes an aromatic epoxy compound having two glycidyl groups in one molecule (hereinafter referred to as a bifunctional aromatic epoxy compound) and two epoxy compounds in one molecule. Using an aromatic alcohol having a phenolic hydroxyl group (hereinafter referred to as a bifunctional aromatic alcohol) as a raw material, polymerization is carried out alternately in a solvent or in the absence of a solvent, using a known esterification catalyst as described below. It can be easily manufactured by the method.
前記二官能芳香族エポキシ化合物としては、 下記式 （A ) 〜 （D ) で示さ れるような芳香環を有するビフエノ一ル型ジグリシジルェ一テル、 ビキシレ ノール型ジグリシジルェ一テル、 ビスフエノール型ジグリシジルエーテル及 ぴナフ夕レン型ジグリシジルエーテルよりなる群から選ばれた少なく とも 1 種の二官能芳香族エポキシ化合物が好適に用いられる。 このような二官能芳 香族エポキシ化合物を、 二官能芳香族アルコールとの交互共重合体における 一方のモノマ一成分とすることにより、 硬化物の強度、 耐熱性、 電気絶縁性 等に優れた多核エポキシ化合物が得られる。  Examples of the bifunctional aromatic epoxy compound include biphenyl-type diglycidyl ethers having aromatic rings represented by the following formulas (A) to (D), bixylenol-type diglycidyl ethers, bisphenol-type diglycidyl ethers and the like. At least one bifunctional aromatic epoxy compound selected from the group consisting of naphthylene-diglycidyl ethers is preferably used. By using such a bifunctional aromatic epoxy compound as one monomer component in an alternating copolymer with a bifunctional aromatic alcohol, a polynuclear compound excellent in strength, heat resistance, electrical insulation, etc. of a cured product is obtained. An epoxy compound is obtained.
Figure imgf000014_0001
Figure imgf000014_0001
式中、 R 3、 R 4 S R 5、 R 6は同一の又は互いに異なる、 水素原子又は炭 素数 1〜4のアルキル基を表わし、 R7、 R8、 R R 1 Qは同一の又は互い に異なる、水素原子、炭素数 1〜4のアルキル基又はハロゲン原子を表わし、 R 1 R 1 2は同一の又は互いに異なる、 水素原子、 メチル基又はハロゲン 化メチル基を表わす。 In the formula, R 3 , R 4 S R 5 and R 6 are the same or different from each other, R 7 , R 8 , and RR 1 Q represent the same or different hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or halogen atoms, and R 1 R 12 represents Represents the same or different hydrogen atom, methyl group or methyl halide group.
前記ビフエノ一ル型、 ビキシレノール型、 ビスフエノール型又はナフタレ ン型のジグリシジルエーテルとしては、 例えばビフヱノール化合物、 ビキシ レノール化合物、 ビスフエノ一ル化合物又はジヒ ドロキシナフタレンとェピ ハロヒ ドリンとの反応から製造されるものを使用することができる。 また、 市販のエポキシ化合物も使用することができ、 例えば、 ビフエノ一ル型ジグ リシジルェ一テルとしてはジャパンエポキシレジン （株） 製の商品名 「ェピ コート YL— 6 0 5 6」 等、 ビキシレノール型ジグリシジルエーテルとして はジャパンエポキシレジン （株） 製の商品名 「ェピコート YX— 4 0 0 0」 等、 ビスフヱノール型ジグリシジルェ一テルとしては旭化成エポキシ （株） 製の商品名 「ァラルダイ ト # 2 6 0」 、 「ァラルダイ ト # 6 0 7 l j 等のビ スフヱノール A型エポキシ化合物、 或いは大日本インキ化学工業 （株） 製の 商品名 「ェピクロン 8 3 0 Sj 等のビスフエノ一ル F型エポキシ化合物、 或 いは大日本ィンキ化学工業 （株） 製の商品名 「ェピクロン E XA 1 5 1 4」 等のビスフヱノ一ル S型エポキシ化合物等、 ナフ夕レン型ジグリシジルェ一 テルとしては大日本インキ化学工業 （株） 製の商品名 「ェピクロン HP— 4 0 3 2 (D) 」 等を挙げることができ、 これらを単独で又は 2種類以上を組 み合わせて使用することができる。  Examples of the biglycol type, bixylenol type, bisphenol type or naphthalene type diglycidyl ether include, for example, a biphenol compound, a bixylenol compound, a bisphenol compound, or a reaction between dihydroxynaphthalene and epihalohydrin. What is manufactured can be used. In addition, commercially available epoxy compounds can also be used. Examples of the biphenyl-type diglycidyl ethers include “Epicoat YL-6056” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). As a diglycidyl ether type, such as "Epicoat YX-400" manufactured by Japan Epoxy Resin Co., Ltd. As a bisphenol type diglycidyl ether, a product name manufactured by Asahi Kasei Epoxy Co., Ltd. "Araldite # 260" And bisphenol A-type epoxy compounds such as Araldite # 607 lj, or bisphenol F-type epoxy compounds such as Epiclone 830 Sj (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) Is a bisphenol S-type epoxy compound such as “Epiclone EXA1514” (trade name) manufactured by Dainippon Ink and Chemicals, Inc. Examples of the diglycidyl ether include “Epiclone HP—4032 (D)” (trade name, manufactured by Dainippon Ink and Chemicals, Inc.). These may be used alone or in combination of two or more. can do.
本発明に使用する二官能芳香族アルコールは、 その構造に特徴があり、 耐 熱性を高くするために芳香環を有し、 対称構造或いは剛直な構造を有したも のを使用することができる。 このような化合物としては、 例えば 1 , 4—ジ ヒ ドロキシナフ夕レン、 1， 5—ジヒ ドロキシナフ夕レン、 1 , 6—ジヒ ド ロキシナフ夕レン、 2 , 6—ジヒ ドロキシナフ夕レン、 2 , 7—ジヒ ドロキ シナフ夕レン、 2 , 8—ジヒ ドロキシナフ夕レン等のジヒ ドロキシナフタレ ン誘導体、 ビキシレノール、 ビフエノール等のビフヱノール誘導体、 ビスフ エノ一ル八、 ビスフエノ一ル5\ ビスフエノール S、 アルキル基置換ビスフ エノ一ル等のビスフエノ一ル誘導体、 ハイ ドロキノン、 メチルハイ ドロキノ ン、 トリメチルハイ ドロキノン等のハイ ドロキノン誘導体などを挙げること ができ、 これらを単独で又は 2種類以上を組み合わせて使用することができ 前記した一般式 （ 6 ) で表わされるエポキシ化合物の中でも、 特に前記一 般式 （ 7 a ) 又は （ 7 b ) で表わされるエポキシ化合物が好ましい。 この一 般式 （ 7 a ) 又は （ 7 b ) で表わされるエポキシ化合物は、 ビフエ二ル型及 び Z又はビキシレノ一ル型のエポキシ化合物又はビスフエノ一ル型エポキシ 化合物と、 1 , 5—、 1 , 6 、 2 , 6—、 2 , 7—置換体等の少なく とも 1種のジヒドロキシナフ夕レンとを原料として、 エーテル化触媒を用い、 溶 媒中又は無溶媒で交互に重合させる方法によって容易に製造することができ る。 ジヒ ドロキシナ,フタレンとしては、 軟化点の高い 1 , 5—、 1， 6—又 は 2 , 6 —置換体、 特に対称的な 1， 5 —及び 2， 6 —置換体を用いること が好ましい。 The bifunctional aromatic alcohol used in the present invention has a feature in its structure. An alcohol having an aromatic ring in order to enhance heat resistance and having a symmetrical structure or a rigid structure can be used. Such compounds include, for example, 1,4-dihydroxyxafene, 1,5-dihydroxyxafene, 1,6-dihydroxyxafene, 2,6-dihydroxyxafene, 2,7— Dihydroxy naphthalene derivatives such as dihydroxy synafene, 2,8-dihydroxy naphthene, biphenol derivatives such as bixylenol and biphenol, and bisphenol Bisphenol derivatives such as phenol 8, bisphenol 5 \ bisphenol S, alkyl-substituted bisphenol, and hydroquinone derivatives such as hydroquinone, methylhydroquinone, and trimethylhydroquinone. These can be used alone or in combination of two or more. Among the epoxy compounds represented by the general formula (6), the epoxy compounds represented by the general formula (7a) or (7b) are particularly preferable. Is preferred. The epoxy compound represented by the general formula (7a) or (7b) includes a biphenyl-type and a Z- or bixylenol-type epoxy compound or a bisphenol-type epoxy compound; , 6,2,6-, 2,7-substituted and at least one dihydroxynaphthylene is used as a raw material and an etherification catalyst is used to alternately polymerize in a solvent or without a solvent. Can be manufactured. As dihydroxyxina and phthalene, it is preferable to use 1,5-, 1,6- or 2,6-substituted compounds having a high softening point, particularly symmetric 1,5- and 2,6-substituted products.
前記一般式 （ 6 ) 及び （ 7 a ) 、 ( 7 b ) で表わされるエポキシ化合物の 合成に使用される触媒としては、 グリシジル基とフヱノール性水酸基が定量 的に反応するホスフィン類、 アルカリ金属化合物、 アミン類を単独で又は併 用して用いるのが好ましい。 これ以外の触媒は、 ゲル化するので好ましくな い。  Examples of the catalyst used for the synthesis of the epoxy compounds represented by the general formulas (6), (7a), and (7b) include phosphines, alkali metal compounds, and glycidyl groups that react quantitatively with phenolic hydroxyl groups. It is preferable to use amines alone or in combination. Other catalysts are not preferable because they cause gelation.
ホスフィン類としては、 ト リブチルホスフィン、 ト リフエニルホスフィ ン 等のト リアルキルもしくはト リアリールホスフィ ン又はこれらと酸化合物と の塩類などが挙げられる。  Examples of the phosphines include trialkyl or triaryl phosphines such as tributyl phosphine and triphenyl phosphine, and salts of these with an acid compound.
アルカリ金属化合物としては、 ナト リウム、 リチウム、 カリウム等のアル 力リ金属の水酸化物、 ハロゲン化物、 アルコラート、 アミ ドなどが挙げられ、 これらを単独で又は 2種類以上を組み合わせて用いることができる。  Examples of the alkali metal compound include hydroxides, halides, alcoholates, and amides of alkali metals such as sodium, lithium, and potassium, and these can be used alone or in combination of two or more. .
アミン類としては、 脂肪族又は芳香族の第一級、 第二級、 第三級、 第四級 アミン類などが挙げられ、 これらを単独で又は 2種類以上を組み合わせて用 いることができる。 アミン類の具体例としては、 ト リエタノールァミン、 N, N—ジメチルビペラジン、 ト リェチルァミン、 ト リー n—プロピルァミン、 へキサメチレンテ トラミン、 ピリジン、 テトラメチルアンモニゥムプロマイ ドなどが挙げられる。 Examples of the amines include aliphatic or aromatic primary, secondary, tertiary, and quaternary amines. These may be used alone or in combination of two or more. Can be. Specific examples of amines include triethanolamine, N, N-dimethylbiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramamine, pyridine, tetramethylammonium bromide and the like. .
これらの触媒は、 前記二官能芳香族エポキシ化合物と二官能芳香族アルコ —ルの総仕込量 1 00質量部に対して、 0. 00 1〜 1質量部、 好ましくは 0. 0 1〜1質量部の範囲で用いることが好ましい。 この理由は、 触媒の使 用量が 0. 00 1,質量部未満では、 反応に時間がかかり経済的でなく、 一方、 1質量部を超えると、逆に反応が早いために制御がしにく くなるからである。 また、二官能芳香族エポキシ化合物と二官能芳香族アルコールとの反応は、 前記触媒の存在下、 不活性ガス気流中又は空気中で 130〜 180 °Cの温度 範囲にて行なうことが好ましい。  These catalysts are used in an amount of 0.001 to 1 part by mass, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol. It is preferably used in the range of parts. The reason for this is that if the amount of catalyst used is less than 0.001 parts by mass, the reaction takes a long time and is not economical, whereas if it exceeds 1 part by mass, the reaction is too fast to control. Because it becomes. The reaction between the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol is preferably carried out in the presence of the catalyst in a stream of inert gas or in air at a temperature in the range of 130 to 180 ° C.
次に、 前記一般式 （ 1 ) 又は （ 8 a) 、 (8 b) で表わされる本発明の多 核エポキシ化合物について説明する。  Next, the polynuclear epoxy compound of the present invention represented by the general formula (1) or (8a) or (8b) will be described.
前記一般式 （ 1 ) 又は （ 8 a) 、 （ 8 b) で表わされる本発明の多核ェポ キシ化合物は、 後述するような公知の溶媒中又は無溶媒下、 アルカリ金属水 酸化物の存在下にて、 前記一般式 （ 6 ) 又は （ 7 a) 、 (7 b) のエポキシ 化合物におけるアルコール性水酸基とェピハロヒ ドリンとを反応させること によって製造することができる。  The polynuclear epoxy compound of the present invention represented by the general formula (1) or (8a) or (8b) may be used in a known solvent or in the absence of a solvent as described below in the presence of an alkali metal hydroxide. The compound can be produced by reacting an alcoholic hydroxyl group in the epoxy compound of the general formula (6) or (7a) or (7b) with ephalohydrin.
前記ェピハロヒ ドリンとしては、 例えばェビクロルヒ ドリン、 ェピブ口ム ヒ ドリン、 ェピョ一ドヒ ドリン、 ?ーメチルェピクロルヒ ドリン、 —メチ ルェピブロムヒ ドリン、 5—メチルェピョードヒ ドリンなどが用いられる。 前記一般式 （ 1 ) 及び （ 8 a) 、 (8 b) で表わされる本発明の多核ェポ キシ化合物において、ェピハロヒ ドリンの使用量は一般式（ 6 )又は（ 7 a)、 (7 b) におけるアルコール性水酸基 1当量に対して 0. 1倍当量以上使用 すればよい。 但し、 前記水酸基 1当量に対して 1 5倍当量を超える量の使用 は、 容積効率が悪くなり好ましくない。 また、 溶媒としては、 ジメチルスルホキシド、 N， N—ジメチルホルムァ ミ ド、 N， N—ジメチルァセ トアミ ド等の非プロ トン性極性溶媒、 トルエン、 キシレン等の芳香族炭化水素類等の公知の溶媒を用いることができるが、 こ れらの中でも非プロ トン性極性溶媒、特にジメチルスルホキシドが好ましい。 この溶媒の使用量は、 一般式 （ 6 ) 又は （ 7 a) 、 (7 b) で表わされるェ ポキシ化合物に対して 5〜 300質量％とすることが好ましい。この理由は、 5質量％未満ではアルコール性水酸基とェピハロヒ ドリンとの反応が遅くな り、 一方、 300質量％を超えると容積効率が悪くなるからである。 As the epihalohydrin, for example, ebichlorhydrin, epibihydr muhydrin, epiohydrin, 1-methylepichlorohydrin, -methylepibromhydrin, 5-methylepihydrhydrin and the like are used. In the polynuclear epoxy compound of the present invention represented by the general formulas (1), (8a), and (8b), the amount of ephalohydrin used may be the general formula (6) or (7a), (7b) May be used in an amount of 0.1 equivalent or more per equivalent of the alcoholic hydroxyl group in the above. However, the use of an amount exceeding 15 equivalents to 1 equivalent of the hydroxyl group is not preferable because the volumetric efficiency is deteriorated. Examples of the solvent include non-protonic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and known solvents such as aromatic hydrocarbons such as toluene and xylene. Among them, a non-protonic polar solvent, particularly, dimethyl sulfoxide is preferable. The amount of the solvent used is preferably 5 to 300% by mass based on the epoxy compound represented by the general formula (6) or (7a) or (7b). The reason for this is that if it is less than 5% by mass, the reaction between the alcoholic hydroxyl group and the ephalohydrin will be slow, while if it exceeds 300% by mass, the volumetric efficiency will be poor.
また、 アルカリ金属水酸化物としては、 苛性ソーダ、 苛性カリ、 水酸化リ チウム、 水酸化カルシウムなどが使用でき、 特に苛性ソーダが好ましい。 こ のアルカリ金属水酸化物の使用量は、 一般式 （6) 又は （7 a) 、 (7 b) で表わされるエポキシ化合物におけるエポキシ化したいアルコール性水酸基 1当量に対して 0. 5〜2倍当量とすることが好ましい。  As the alkali metal hydroxide, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, and caustic soda is particularly preferable. The amount of the alkali metal hydroxide used is 0.5 to 2 times the equivalent of the alcoholic hydroxyl group to be epoxidized in the epoxy compound represented by the general formula (6) or (7a) or (7b). It is preferable to make it equivalent.
前記一般式 （6) 又は （7 a) 、 (7 b) で表わされるエポキシ化合物に おけるアルコール性水酸基とェピハロヒ ドリンとの反応温度は、 20°C以上、 好ましくは 30°C以上、 100°C以下の範囲が好ましい。 この理由は、 反応 温度が 20°C未満であると反応速度が遅くなって反応に要する時間が長くな り、 一方、 反応温度が 100°Cを超えると副反応が多く起こり好ましくない からである。  The reaction temperature between the alcoholic hydroxyl group and the epihalohydrin in the epoxy compound represented by the general formula (6) or (7a) or (7b) is 20 ° C. or higher, preferably 30 ° C. or higher, 100 ° C. The following ranges are preferred. The reason for this is that if the reaction temperature is lower than 20 ° C, the reaction rate becomes slower and the time required for the reaction becomes longer, while if the reaction temperature exceeds 100 ° C, many side reactions occur, which is not preferable. .
前記一般式 （6) 又は （7 a) 、 (7 b) で表わされるエポキシ化合物に おけるアルコール性水酸基とェピハロヒ ドリンとの反応は、 ジメチルスルホ キシド又は四級アンモニゥム塩などの第 4級塩基性塩化合物又は 1， 3—ジ メチルー 2—ィ ミダゾリンとアル力リ金属水酸化物の共存下、 該ァルカリ金 属水酸化物の量を調整することにより行なうこともできる。 その際、 溶剤と してメタノールやエタノール等のアルコール類、 トルエン、 キシレン等の芳 香族炭化水素類、 メチルイソプチルケトン、 メチルェチルケトン等のケトン 類、テトラヒ ドロフラン等の環状ェ一テル化合物などを併用しても構わない。 用い得る第 4級塩基性塩化合物の具体例としては、 例えばテトラメチルァ ンモニゥムク口ライ ド、 テトラプチルアンモニゥムブロマイ ド、 ト リメチル ペンジルアンモニゥムハライ ド、 テ トラメチルアンモニゥムバイカーボネー ト、 テトラメチルアンモニゥムベンゾェ一ト、 テトラメチルアンモニゥムハ イ ド口オキサイ ド、 テ トラエチルアンモニゥムハイ ド口オキサイ ド、 テ トラ メチルホスホニゥムハイ ドロォキサイ ド等が挙げられる。 但し、 上記の触媒 は単独で又は 2種類以上を混合して用いることができる。 その使用量は前記 一般式 （ 6 ) 又は （ 7 a) 、 ( 7 b) で表わされるエポキシ化合物の水酸基The reaction between the alcoholic hydroxyl group and the ephalohydrin in the epoxy compound represented by the general formula (6) or (7a) or (7b) is carried out by a quaternary basic salt such as dimethyl sulfoxide or a quaternary ammonium salt. It can also be carried out by adjusting the amount of the alkali metal hydroxide in the presence of a compound or 1,3-dimethyl-2-imidazoline and an alkali metal hydroxide. At that time, alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, and cyclic ether compounds such as tetrahydrofuran are used as solvents. You may use together. Specific examples of quaternary basic salt compounds that can be used include, for example, Nummonium mouthride, tetrabutylammonium bromide, trimethylpennylammonium halide, tetramethylammonium bicarbonate, tetramethylammonium benzoate, tetramethylammonium benzoate Oxide oxide at the mouth, tetraethylammonium hydroxide oxide at the mouth, tetramethylphosphonimide hydroxide, and the like. However, the above catalysts can be used alone or in combination of two or more. The amount used is the hydroxyl group of the epoxy compound represented by the general formula (6) or (7a) or (7b).
1当量に対して、 0. 00 1〜2当量の範囲が好ましい。 より好ましくは 0.The range of 0.001 to 2 equivalents to 1 equivalent is preferable. More preferably 0.
0 5〜0. 2当量の範囲である。 0. 0 0 1当量未満の場合はその効果が発 現し難く、 原料として使用するエポキシ化合物のグリシジルエーテル基がェ ポキシ化合物の水酸基と反応して高分子量化したりするので好ましくない。 一方、 2当量を越える量を添加しても、 それ以上の格別な効果の向上は見ら れない。 The range is from 0.5 to 0.2 equivalents. If the amount is less than 0.001 equivalent, the effect is hardly exhibited, and the glycidyl ether group of the epoxy compound used as a raw material reacts with the hydroxyl group of the epoxy compound to increase the molecular weight, which is not preferable. On the other hand, even if the amount exceeds 2 equivalents, no further improvement in the effect is seen.
このようにして得られる本発明の多核エポキシ化合物は、 数平均分子量で 400〜 5 000、 好ましくは 5 0 0〜 3 0 00、 より好ましくは 5 0 0〜 2 00 0である。 当該エポキシ化合物の数平均分子量が 40 0未満では、 得 られる硬化物の強靱性が充分でなく、 一方、 5 0 0 0を超えると溶媒に対す る溶解性が低下するので好ましくない。  The polynuclear epoxy compound of the present invention thus obtained has a number average molecular weight of 400 to 5,000, preferably 500 to 300,000, more preferably 500 to 200,000. When the number average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is not sufficient. On the other hand, when it is more than 500, the solubility in a solvent is lowered, which is not preferable.
エポキシ化率は、 目的に応じて （所望の物性に応じて）適宜選択できるが、 1 0〜： L 0 0 %が適当であり、 好ましくは 3 0〜 9 0 %、 より好ましくは 4 0 ~ 8 0 %である。  The epoxidation ratio can be appropriately selected depending on the purpose (depending on desired physical properties), but is preferably from 10 to L 0%, preferably from 30 to 90%, more preferably from 40 to 90%. 80%.
本発明の多核エポキシ化合物は、 単独で又は他のエポキシ樹脂との組合せ で用いられ、 通常のエポキシ樹脂の場合と同様に、 硬化剤さらに必要により 硬化促進剤等を添加して硬化させることができる。  The polynuclear epoxy compound of the present invention is used alone or in combination with another epoxy resin, and can be cured by adding a curing agent and, if necessary, a curing accelerator or the like, as in the case of a normal epoxy resin. .
エポキシ樹脂としては、 後に例示するような従来公知の各種エポキシ樹脂 (D) を単独で又は 2種以上を組み合わせて用いることができる。  As the epoxy resin, various known epoxy resins (D) as exemplified later can be used alone or in combination of two or more.
使用する硬化剤としては、 アミン系化合物、 酸無水物系化合物、 アミ ド系 化合物、 フエノール系化合物などが挙げられる。 具体例としては、 ジァミノ ジフエニルメタン、 ジエチレント リアミン、 ト リエチレンテトラミン、 ジァ ミノジフエニルスルホン、 イソホロンジアミン、 ジシアンジアミ ド、 リノレ ン酸の 2量体とエチレンジアミンとより合成されるポリアミ ド榭脂、 無水フ タル酸、 無水ト リメ リ ッ ト酸、 無水ピロメ リ ッ ト酸、 無水マレイン酸、 テ ト ラヒ ドロ無水フ夕ル酸、 メチルテトラヒ ドロ無水フ夕ル酸、 無水メチルナジ ック酸、 へキサヒ ドロ無水フ夕ル酸、 メチルへキサヒ ドロ無水フ夕ル酸、 フ エノ一ルノボラヅク、 及びこれらの変性物、 イ ミダゾ一ル、 B F 3 —アミン 錯体、 グァニジン誘導体などが挙げられる。 これらの硬化剤はそれそれ単独 で用いてもよいし、 2種以上を組み合わせて用いてもよい。 Examples of the curing agent used include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. A specific example is Jamino Polyamide resin synthesized from diamine of diphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride To acid anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrofluoric anhydride, methyltetrahydrofluoric anhydride, methylnadic anhydride, hexahydrofluoric anhydride, methyl Examples thereof include xahydrofluoric anhydride, phenol novolak, and modified products thereof, imidazole, BF 3 -amine complex, and guanidine derivative. These curing agents may be used alone or in combination of two or more.
硬化促進剤としては、 例えばイ ミダゾ一ル類、 第 3級ァミン類、 フヱノ一 ル類、 金属化合物等が挙げられる。  Examples of the curing accelerator include imidazoles, tertiary amines, phenols, and metal compounds.
このように、 本発明の多核エポキシ化合物、 硬化剤、 さらに必要により硬 化促進剤等が配合されたエポキシ樹脂組成物は、 従来から知られている方法 と同様の条件で容易にエポキシ樹脂組成物の硬化物とすることができる。 例 えば、 本発明の多核エポキシ化合物、 硬化剤、 充填剤及びその他の添加剤を 混合し、 必要に応じて押出機やニーダ一、 ロール等を用いて均一になるまで 充分に混練してエポキシ樹脂組成物を得、 このエポキシ樹脂組成物を溶融し た後、 注型あるいはトランスファ一成形機などを用いて成形し、 さらに 8 0 〜 2 0 0 °Cに加熱することにより硬化物を得ることができる。 また、 ェポキ シ樹脂組成物を溶剤に溶解させ、 ガラス繊維、 カーボン繊維、 ポリエステル 繊維、 ポリアミ ド繊維、 アルミナ繊維、 紙などの基材に含浸させ、 加熱乾燥 して得たプリプレグを、 熱プレス成形して硬化物を得ることもできる。  As described above, the epoxy resin composition containing the polynuclear epoxy compound of the present invention, the curing agent, and if necessary, the curing accelerator, etc., can be easily prepared under the same conditions as conventionally known methods. Cured product. For example, the polynuclear epoxy compound of the present invention, a curing agent, a filler, and other additives are mixed, and if necessary, sufficiently kneaded using an extruder, a kneader, a roll, or the like, until the epoxy resin is mixed. After the composition is obtained and the epoxy resin composition is melted, molded using a casting machine or a transfer molding machine, and then further heated to 80 to 200 ° C. to obtain a cured product. it can. In addition, a prepreg obtained by dissolving the epoxy resin composition in a solvent, impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating is subjected to hot press molding. To obtain a cured product.
なお、 上記エポキシ樹脂組成物では、 必要に応じて無機充填剤又は有機充 填剤等の種々の配合剤を添加することができる。  In the epoxy resin composition, various additives such as an inorganic filler and an organic filler can be added as needed.
また、 本発明の多核エポキシ化合物、 硬化剤、 さらに必要により硬化促進 剤等が配合されたェポキシ樹脂組成物を溶剤に溶解させ、 塗布方法に適した 粘度に調整することができる。  Further, the epoxy resin composition containing the polynuclear epoxy compound of the present invention, the curing agent, and, if necessary, the curing accelerator and the like can be dissolved in a solvent to adjust the viscosity to a suitable one for the coating method.
このような溶剤としては、 例えば、 メチルェチルケトン、 シクロへキサノ ン等のケトン類； トルエン、 キシレン、 テトラメチルベンゼン等の芳香族炭 化水素類 ； セロソルブ、 メチルセ口ソルプ、 プチルセ口ソルブ、 カルビトー ル、 メチルカルビトール、 ブチルカルビトール、 プロピレングリコールモノ メチルエーテル、 プロピレングリコールモノェチルエーテル、 ジプロピレン グリコ一ルジェチルエーテル、 トリエチレングリコールモノェチルエーテル 等のグリコ一ルェ一テル類； 酢酸ェチル、 酢酸ブチル、 セロソルブァセテー ト、 ブチルセ口ソルブアセテート、 カルビト一ルアセテート、 プチルカルビ ト一ルァセテ一ト、 プロピレングリコールモノメチルエーテルアセテート、 ジプロビレングリコールモノメチルエーテルァセテ一ト等の酢酸エステル 類； エタノール、 プロパノール、 エチレングリコ一ル、 プロピレングリコ一 ル等のアルコール類；オクタン、 デカン等の脂肪族炭化水素；石油エーテル、 石油ナフサ、 水添石油ナフサ、 ソルベントナフサ等の石油系溶剤等が挙げら れる。 これらの有機系溶剤は、 単独で又は 2種類以上の混合物として使用で ぎる。 Such solvents include, for example, methyl ethyl ketone, cyclohexano Ketones such as toluene; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl sorb, butyl sorb, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycoyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc .; ethyl acetate, butyl acetate, cellosolve acetate, butylacetosolve acetate, carbitol acetate Acetates such as butylcarbyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; ethanol, propanol, and ethyl acetate Nguriko Ichiru, alcohols such as propylene glycol one le; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha like et be. These organic solvents can be used alone or as a mixture of two or more.
さらに本発明者らの研究によると、 前記のような線状の多核エポキシ化合 物、 特に軟化点の高いビフヱニル骨格とナフタレン骨格、 あるいはビスフエ ノール骨格とナフ夕レン骨格とが交互に共重合された交互共重合型の線状多 核エポキシ化合物に、 不飽和基含有モノカルボン酸 （ c ) を反応させて得ら れる下記一般式 （ 2 a ) 又は （ 2 b ) で表わされる多核エポキシァクリ レ一 ト化合物 （b ) が、 光硬化及び熱硬化のいずれも可能であり、 しかもこのよ うな硬化処理によって優れた耐熱性と強靱性を併せ持つ硬化物を与えること が見出された。  Further, according to the study of the present inventors, linear polynuclear epoxy compounds as described above, in particular, a biphenyl skeleton and a naphthalene skeleton having a high softening point, or a bisphenol skeleton and a naphthylene skeleton were alternately copolymerized. A polynuclear epoxy acrylate represented by the following general formula (2a) or (2b) obtained by reacting an unsaturated copolymer-containing monocarboxylic acid (c) with an alternating copolymer type linear polynuclear epoxy compound. It has been found that the compound (b) is capable of both photo-curing and thermo-curing, and that such a curing treatment gives a cured product having both excellent heat resistance and toughness.
0 Z 0 Z
Z ' —〇一 X— 0- ■C H 2 — C H— C H2— 0— Y— 0- ΖZ '—〇 一 X— 0- ■ CH 2 — CH— CH 2 — 0— Y— 0- CH
CH2— CH— C H2— 0— X— 0- -Z' · · · ( 2 a) CH 2 — CH— CH 2 — 0— X— 0- -Z '· · (2 a)
n OZ n OZ
CH2— CH- ■CH2一〇一 X— 0- -CH2— CH— CH2— 0— Y— 0— CH 2 — CH- ■ CH 2 1〇1 X— 0- -CH 2 — CH— CH 2 — 0— Y— 0—
\ /  \ /
〇  〇
0Z  0Z
-CH2— CH— CH2— 0— X— 0- — CH2— CH— CHi (2b) n \ / -CH 2 — CH— CH 2 — 0— X— 0- — CH 2 — CH— CHi (2b) n \ /
0  0
式中、 Xと Yは異なる芳香環を表わし、 Xはビフエノール型ジグリシジル エーテル、 ビキシレノール型ジグリシジルエーテル、 ビスフエノール型ジグ リシジルェ一テル及びナフ夕レン型ジグリシジルェ一テルよりなる群から選 ばれた少なく とも 1種の 1分子中に 2個のグリシジル基を有する芳香族ェポ キシ化合物の芳香環残基を表わし、 Υはジヒ ドロキシナフ夕レン及びその誘  In the formula, X and Y represent different aromatic rings, and X is at least one selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether. Both represent the aromatic ring residue of an aromatic epoxy compound having two glycidyl groups in one molecule, and Υ indicates dihydroxynaphthylene and its derivative.
C  C
導体、 ビフエノ一ル及びその誘導体、 ビキシレノー Hル及びその誘導体、 ビス フエノ一ル及びその誘導体、 及びハイ ドロキノン及びそ Cの誘導体よりなる群 Group consisting of conductors, biphenol and its derivatives, bixylenol H and its derivatives, bisphenol and its derivatives, and hydroquinone and its derivatives C
\一o  \ One o
かち選ばれた少なく とも 1種の 1分子中に 2個のフエノール性水酸基を有すAt least two phenolic hydroxyl groups in one selected molecule
/ C  / C
H  H
る芳香族アルコールの芳香環残基を表わし、 Ζは互いに無関係に、 下記一般 式 （3) もしくは （4) で示される基又は水素原子を表わし、 かつ Ζの少な く とも 1個は一般式 （3) で示される基であり、 Ζ， は互いに無関係に、 下 記一般式 （3， ) もしくは （4， ) で示される基を表わし、 ηは 1〜20の 整数を表わす。 Represents an aromatic ring residue of an aromatic alcohol represented by the following formula: Ζ independently of each other represents a group represented by the following general formula (3) or (4) or a hydrogen atom, and at least one of the は represents the general formula ( 3), wherein Ζ and 、 independently of each other represent a group represented by the following general formula (3,) or (4,), and η represents an integer of 1 to 20.
R1 〇 R1 R 1 〇 R 1
I II  I II
一 CH2 — C一 CH2 - 0 - C— R: ... (3) · (4) One CH 2 - C one CH 2 - 0 - C- R: ... (3) · (4)
0H  0H
0  0
一 CH2 -CH-CHZ -0-C-R2 · (3' ) CH2 -CH-CHi (4' ) 1 CH 2 -CH-CH Z -0-CR 2 (3 ') CH 2 -CH-CHi (4')
I \ /  I \ /
OH 0  OH 0
式中、 R1は水素原子又はメチル基を表わし、 R2は不飽和モノカルボン酸 残基を表わす。 In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an unsaturated monocarboxylic acid residue.
すなわち、 本発明の多核エポキシァクリレート化合物 （b) は、 上記一般 式 （2 a) 又は （2 b) で表わされるように異種の芳香璟を規則的に繰り返 し含有するため、 機械的強度の高い硬化物が得られ、 また線状構造としたこ とによって、 また多核エポキシ化合物に不飽和基含有モノカルボン酸を反応 させたことによって、 光硬化又は熱硬化によつて耐熱性の高い硬化物が得ら れると共に、 基材に対する密着性、 耐水性、 耐薬品性、 電気絶縁性、 成形性 に優れた硬化物が得られるものである。 That is, the polynuclear epoxy acrylate compound (b) of the present invention regularly repeats different types of aromatic compounds as represented by the general formula (2a) or (2b). As a result, a cured product with high mechanical strength is obtained, and a linear structure is used, and a polycarboxylic epoxy compound is reacted with an unsaturated group-containing monocarboxylic acid, so that photocuring or heat curing is performed. As a result, a cured product having high heat resistance can be obtained, and a cured product having excellent adhesion to a substrate, water resistance, chemical resistance, electrical insulation, and moldability can be obtained.
より具体的な好適な態様は、 下記一般式 （ 9 a) 〜 （ 9 d) で示される多 核エポキシァクリレート化合物である。  More specific preferred embodiments are polynuclear epoxy acrylate compounds represented by the following general formulas (9a) to (9d).
Figure imgf000023_0001
Figure imgf000023_0001
(9c)
Figure imgf000023_0002
Figure imgf000024_0001
(9c)
Figure imgf000023_0002
Figure imgf000024_0001
式中、 R3〜R12、 Z及び nは前記と同じ意味を有する。 In the formula, R 3 to R 12 , Z and n have the same meaning as described above.
好適な態様においては、 〜： R6が全て水素原子であるか、 又は R3〜RIn a preferred embodiment,-: R 6 is all hydrogen atoms, or R 3 -R
6が全てメチル基であり、 また R7〜R 1 Dが全て水素原子、 R11及び R12が 6 are all methyl groups, R 7 to R 1 D are all hydrogen atoms, R 11 and R 12 are
Π  Π
全てメチル基であり、 一方、 二価のナフ夕 cレ Hン環残基が 1， 5—、 1， 6—、All are methyl groups, while the divalent naphthyl radical is a 1,5-, 1,6-,
2, 6—又は 2， 7—置換体である。 特に好適な態様においては、 前記 R3 c 2,6- or 2,7-substituted. In a particularly preferred embodiment, the R 3 c
~R6は全てメチル基であり、 かつ前記二価のナフ \ H夕 oレン環残基は 1 , 5—、 ~ R 6 are all methyl groups, and the divalent naph \ H
\ c  \ c
1 , 6—、 又は 2， 6—置換体である。 H  1, 6- or 2,6-substituted. H
前記一般式 （2 a) 又は （2 b) で示される多核エポキシァクリレート化 合物 （b) は、 下記一般式 （ 10) で示される多核エポキシ化合物に不飽和 基含有モノカルボン酸 （c) を、 前述した有機溶剤の存在下あるいは非存在 下、 重合禁止剤や反応触媒の共存下、 反応させて得ることができる。  The polynuclear epoxy acrylate compound (b) represented by the general formula (2a) or (2b) is obtained by adding an unsaturated group-containing monocarboxylic acid (c) to the polynuclear epoxy compound represented by the following general formula (10). ) In the presence or absence of the aforementioned organic solvent, in the presence of a polymerization inhibitor or a reaction catalyst.
0Z1 0Z 1
CH2— CH- -CH: -0—： 一 0- -CH2— CH— CH2— 0— Y— 0— CH 2 — CH- -CH : -0—: 1 0- -CH 2 — CH— CH 2 — 0— Y— 0—
\ /  \ /
0  0
OZ1 OZ 1
■CH: -CH— CH2— 0— X— 0- (10) ■ CH : -CH— CH 2 — 0— X— 0- (10)
式中、 X、 Y及び nは前記と同じ意味を有し、 Z 1は互いに無関係に水素 原子又は前記一般式 （4) で示される基である。 In the formula, X, Y and n have the same meaning as described above, and Z 1 is independently of each other a hydrogen atom or a group represented by the general formula (4).
前記一般式 （ 10) で示される多核エポキシ化合物に、 不飽和基含有モノ カルボン酸（ c) を反応させて不飽和多核エポキシァクリレート化合物 （b) を得るにあたっては、 前記一般式（ 10)で示される多核エポキシ化合物に、 該化合物中に含まれるエポキシ基 1モルに対して不飽和基含有モノカルボン 酸を 0 . 8〜 1 . 3モルの割合で配合し、 不活性溶媒中又は無溶剤で、 約 6 0 ~ 1 5 0 °C、 好ましくは 7 0〜： L 3 0 °Cに加熱して、 好ましくは空気の存 在下に反応を行なう。 反応中の重合によるゲル化を防止するため、 メチルハ ィ ドロキノン、 ノヽィ ドロキノン等のハイ ドロキノン類 ； p —ペンゾキノン、 - トルキノン等のベンゾキノン類などの公知慣用の重合禁止剤を用いるの が好ましい。 また、 反応時間を短縮するために、 エステル化触媒を用いるの が好ましい。 エステル化触媒としては、 例えば、 N , N—ジメチルァニリ ン、 ピリジン、 ト リェチルアミン等の三級アミン及びその塩酸塩又は臭素酸塩； テトラメチルアンモニゥムクロライ ド、 ト リェチルベンジルアンモニゥムク 口ライ ド等の四級アンモニゥム塩 ； パラ トルエンスルホン酸等のスルホン 酸； ジメチルスルホキシド、 メチルスルホキシド等のスルホニゥム塩； 2— ェチルー 4—メチルイ ミダゾ一ル等のィ ミダゾール化合物 ； トリフヱニルホ スフイン、 ト リ _ n—プチルホスフィン等のホスフィ ン類 ；塩化リチウム、 臭化リチウム、 塩化第一錫、 塩化亜鉛等の金属ハロゲン化物などの公知慣用 のものを用いることができる。 不活性溶剤としては、 例えばトルエン、 キシ レンなどを用いることができる。 In order to obtain an unsaturated polynuclear epoxy acrylate compound (b) by reacting an unsaturated group-containing monocarboxylic acid (c) with the polynuclear epoxy compound represented by the general formula (10), In the polynuclear epoxy compound represented by An unsaturated group-containing monocarboxylic acid is compounded in a ratio of 0.8 to 1.3 mol per 1 mol of the epoxy group contained in the compound, and is mixed with an inert solvent or without a solvent in about 60 to 15 mol. 0 ° C., preferably 70 ° C .: Heat to L 30 ° C., and carry out the reaction, preferably in the presence of air. In order to prevent gelation due to polymerization during the reaction, it is preferable to use a known and commonly used polymerization inhibitor such as a hydroquinone such as methylhydroquinone or nitroquinone; or a benzoquinone such as p-benzoquinone or -toluquinone. In order to shorten the reaction time, it is preferable to use an esterification catalyst. Examples of the esterification catalyst include tertiary amines such as N, N-dimethylaniline, pyridine, and triethylamine, and hydrochlorides and bromates thereof; tetramethylammonium chloride, and tribenzylbenzyl ammonium chloride. Quaternary ammonium salts such as sulfide; sulfonic acids such as para-toluenesulfonic acid; sulfonium salts such as dimethyl sulfoxide and methyl sulfoxide; imidazole compounds such as 2-ethyl-4-methylimidazole; triphenylphosphine, tri-n- Known and commonly used phosphines such as butylphosphine; metal halides such as lithium chloride, lithium bromide, stannous chloride, and zinc chloride can be used. As the inert solvent, for example, toluene, xylene and the like can be used.
前記不飽和基含有モノカルボン酸 （ c ) の代表的なものとしては、 ァクリ ル酸、 メタァク リル酸、 ヒ ドロキシェチル （メタ） ァクリレート、 ヒ ドロキ シプロピル （メタ） ァク リ レート、 ヒ ドロキシブチル （メタ） ァクリ レ一ト、 トリメチロールプロパンジ （メタ） ァクリレート、 ペン夕エリスリ ト一ルト リ （メ夕） ァク リ レート、 ジペン夕エリスリ ト一ルペン夕 （メタ） ァク リ レ ート、 フエニルグリシジル （メタ） ァクリレート、 （メ夕） アクリル酸カプ 口ラク トン付加物など水酸基含有ァクリレートの不飽和二塩基酸無水物付加 物などが挙げられる。 ここで特に好ましいのはアクリル酸、 メタアクリル酸 である。 これら不飽和基含有モノカルボン酸は単独で又は 2種以上を混合し て用いることができる。  Representative examples of the unsaturated group-containing monocarboxylic acid (c) include acrylic acid, methacrylic acid, hydroxyshethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth). Acrylate, trimethylolpropane (meta) acrylate, pen erythritol (meta) acrylate, dipentyl erythritol, pen (meta) acrylate, phenylglycidyl (Meth) acrylate, (meth) unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as acrylic acid cap lactone adducts. Here, particularly preferred are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.
本発明の多核エポキシァクリ レート化合物 （b ) の数平均分子量は、 4 0 0〜1 0， 0 0 0、 好ましくは 5 0 0〜7， 0 0 0、 より好ましくは 5 0 0 〜5 , 0 0 0である。 エポキシ化合物の数平均分子量が 4 0 0未満では、 得 られる硬化物の強靱性が充分でなく、 一方、 1 0 , 0 0 0を超えると溶媒に 対する溶解性が低下するので好ましくない。 The number average molecular weight of the polynuclear epoxy acrylate compound (b) of the present invention is 40%. 0 to 100, 0000, preferably 500 to 7,000, more preferably 500 to 5,000. If the number average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is not sufficient. On the other hand, if it exceeds 100,000, the solubility in a solvent decreases, which is not preferable.
本発明の多核エポキシァクリレート化合物は、 単独で又は他のエポキシ樹 脂との併用で、 通常のエポキシ化合物の場合と同様に、 硬化剤さらに必要に より硬化促進剤等を添加することにより熱硬化させることができる。  The polynuclear epoxy acrylate compound of the present invention can be used alone or in combination with other epoxy resins, by adding a curing agent and, if necessary, a curing accelerator, etc., as in the case of ordinary epoxy compounds. Can be cured.
エポキシ樹脂としては、 後に例示するような従来公知の各種エポキシ樹脂 ( D ) を単独で又は 2種以上を組み合わせて用いることができる。 また、 硬 化剤及び硬化促進剤としては先に例示したような従来公知の各種化合物を用 いることができる。  As the epoxy resin, various conventionally known epoxy resins (D) as exemplified later can be used alone or in combination of two or more. Further, as the hardening agent and the hardening accelerator, conventionally known various compounds as exemplified above can be used.
また、 本発明の多核エポキシァクリレート化合物は、 単独で又は他の感光 性 （メタ） ァクリレート化合物との併用で、 通常の感光性 （メタ） ァクリレ —ト化合物の場合と同様に、 光重合開始剤を配合して、 活性エネルギー線の 照射により硬化させることができる。  The polynuclear epoxy acrylate compound of the present invention may be used alone or in combination with another photosensitive (meth) acrylate compound to initiate photopolymerization in the same manner as in the case of a normal photosensitive (meth) acrylate compound. The composition can be cured by irradiation with active energy rays.
他の感光性 （メタ） ァクリレ一ト化合物及び光重合開始剤としては、 後に 例示するような従来公知の各種感光性 （メタ） ァクリレート化合物 （B ) 及 ぴ光重合開始剤 （C ) を用いることができる。  As other photosensitive (meth) acrylate compounds and photopolymerization initiators, various conventionally known photosensitive (meth) acrylate compounds (B) and photopolymerization initiators (C) may be used as exemplified later. Can be.
さらに、 前記した多核エポキシァクリレート化合物は、 単独で又は他の感 光性 （メタ） ァク.リレー ト化合物との併用で、 有機過酸化物ゃァゾ化合物な どによる加熱重合法、 有機過酸化物と促進剤による常温重合法によって硬化 させることができる。  Further, the above-mentioned polynuclear epoxy acrylate compound may be used alone or in combination with another photosensitive (meth) acrylate compound, by a heat polymerization method using an organic peroxide diazo compound or the like. It can be cured by a room temperature polymerization method using a peroxide and an accelerator.
有機過酸化物としては、 t一プチルパ一ォキシペンゾェ一ト、 t—ブチル パーォキシ一 2—ェチルへキサノエート、 ベンゾィルパーオキサイ ド、 シク 口へキサノンパーオキサイ ド、 メチルェチルケトンパーオキサイ ド、 ビス一 4一 t—ブチルシク口へキシルパーォキシジカーボネートなどが挙げられ、 これらを単独で又は 2種以上を組み合わせて用いることができる。 ァゾ化合 物としては、 ァゾビスイソプチルロニトリルなど公知のものを単独で又は 2 種以上を組み合わせて用いることができる。 Organic peroxides include t-butylperoxypentoxide, t-butylperoxy-12-ethylhexanoate, benzoyl peroxide, cyclohexanone peroxide, and methylethyl ketone peroxide. And bis-41-t-butylcyclohexylperoxydicarbonate. These can be used alone or in combination of two or more. As the azo compound, a known compound such as azobisisobutyltylonitrile alone or 2 More than one species can be used in combination.
促進剤としては、 コバルト、 鉄、 マンガンなどのォクチル酸、 ナフテン酸 の塩などの多価金属の塩類、 ジメチルァニリン、 ジェチルァニリン、 p— ト ルイジン、 エタノールアミンなどの有機アミン類など公知のものを単独で又 は 2種以上を組み合わせて用いることができる。  Known accelerators include salts of polyvalent metals such as salts of octylic acid and naphthenic acid such as cobalt, iron and manganese, and organic amines such as dimethylaniline, getylaniline, p-toluidine and ethanolamine. They can be used alone or in combination of two or more.
このように、 本発明の多核エポキシァクリレート化合物、 光重合開始剤、 硬化剤、 さらに必要により硬化促進剤等が配合されたエポキシァクリレート 樹脂組成物は、 従来知られている方法と同様の方法で容易にエポキシァクリ レート樹脂組成物の硬化物を得ることができる。 例えば、 本発明の多核ェポ キシァクリレート化合物と硬化剤、 充填剤及びその他の添加剤とを必要に応 じて押出機、 ニーダ、 口一ル等を iiいて均一になるまで充分に混合してェポ キシァクリレート樹脂組成物を得、 そのエポキシァクリレート樹脂組成物を 溶融後、 注型あるいはトランスファ一成形機などを用いて成形し、 さらに 2 0〜 2 0 0 °Cに加熱することにより硬化物を得ることができる。 また、 ェポ キシァクリレ一ト樹脂組成物を溶剤に溶解させ、 ガラス繊維、 力一ボン繊維、 ポリエステル繊維、 ポリアミ ド繊維、 アルミナ繊維、 紙などの基材に含浸さ せ、 加熱乾燥して得たプリプレグを、 熱プレス成形、 又は活性エネルギー線 を照射して硬化物を得ることもできる。  As described above, the epoxy acrylate resin composition of the present invention in which the polynuclear epoxy acrylate compound, the photopolymerization initiator, the curing agent, and, if necessary, the curing accelerator, etc. are blended, is the same as the conventionally known method. A cured product of the epoxy acrylate resin composition can be easily obtained by the above method. For example, the polynuclear epoxy acrylate compound of the present invention and a curing agent, a filler, and other additives may be sufficiently mixed, if necessary, with an extruder, a kneader, a mouth, etc. until uniform. After obtaining the epoxy acrylate resin composition, the epoxy acrylate resin composition is melted, molded using a casting or transfer molding machine, and further heated to 20 to 200 ° C. to obtain a cured product. Can be obtained. Further, the epoxy acrylate resin composition was dissolved in a solvent, impregnated into a base material such as glass fiber, nylon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and then heated and dried. The cured product can be obtained by subjecting the prepreg to hot press molding or irradiation with active energy rays.
なお、 上記エポキシァクリレート樹脂組成物では、 必要に応じて無機又は 有機充填剤等の種々の配合剤を混合することができる。  In the epoxy acrylate resin composition, various additives such as an inorganic or organic filler can be mixed as necessary.
また、 本発明の多核エポキシァクリレート化合物、 光重合開始剤、 硬化剤、 さらに必要により硬化促進剤等が配合されたエポキシァクリレート樹脂組成 物を溶剤に溶解させ、 塗布方法に適した粘度に調整することができる。  Further, an epoxy acrylate resin composition containing the polynuclear epoxy acrylate compound of the present invention, a photopolymerization initiator, a curing agent, and, if necessary, a curing accelerator, etc. is dissolved in a solvent, and a viscosity suitable for a coating method is obtained. Can be adjusted.
さらに本発明者らの研究によれば、 前記のような異種の芳香環を規則的に 繰り返し含有する線状エポキシ化合物、 特に軟化点の高いビフエ二ル骨格と ナフタレン骨格、 あるいはビスフエノール骨格とナフタレン骨格とが交互に 共重合された交互共重合型の線状エポキシ化合物における側鎖のアルコール 性水酸基に溶媒の存在下でェピハロヒ ドリンを反応させて得られたエポキシ 化合物に、 不飽和基含有モノカルボン酸を反応させ、 得られたエポキシァク リレート化合物に多塩基酸無水物を反応させて得られるアル力リ可溶性の活 性エネルギー線硬化性樹脂が、 高温下における熱安定' liに優れ、 バランスの とれた耐熱性と強靭性を有すること、 及びこのような活性エネルギー線硬化 性樹脂を光硬化性成分として含有する樹脂組成物が、 耐熱性、 密着性、 耐無 電解めつき性、 電気特性、 フレキシブル性、 耐吸湿性並びに PC τ (プレツ シヤークッ力一） 耐性等の特性に優れる硬化物を与えることが見出された。 すなわち、本発明の活性エネルギー線硬化性樹脂（A)は、下記一般式（ 5 ) で示される多核エポキシ化合物 （ a' ) に不飽和基含有モノカルボン酸 （ c ) を反応させ、 得られるエポキシァクリレート化合物 （b， ) にさらに多塩基 酸無水物 （d) を反応させたことによって光硬化性とアルカリ現像性を付与 したものであるが、 異種の芳香環を規則的に繰り返し含有するため機械的強 度の高い硬化物が得られ、 また線状構造としたことによって、 耐熱性の高い 硬化物が得られると共に基材に対する密着性、耐無電解めつき性、電気特性、 フレキシブル性、 耐吸湿性並びに P CT (プレッシャークッ力一） 耐性等に 優れた硬化物が得られるものである。 Further, according to the study of the present inventors, a linear epoxy compound containing the above-mentioned heterogeneous aromatic rings regularly and repeatedly, particularly a biphenyl skeleton and a naphthalene skeleton having a high softening point, or a bisphenol skeleton and a naphthalene Epoxy obtained by reacting ephalohydrin in the presence of a solvent with the alcoholic hydroxyl group in the side chain in an alternating copolymerization type linear epoxy compound in which the skeleton is copolymerized alternately. The compound is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting epoxy acrylate compound is reacted with a polybasic acid anhydride. It is excellent in stability, has well-balanced heat resistance and toughness, and the resin composition containing such an active energy ray-curable resin as a photocurable component has heat resistance, adhesion, and non-resistance. It has been found that a cured product having excellent properties such as electrolytic plating property, electrical properties, flexibility, moisture absorption resistance and PC τ (pre-shearing force) resistance is provided. That is, the active energy ray-curable resin (A) of the present invention is obtained by reacting a polynuclear epoxy compound (a ′) represented by the following general formula (5) with an unsaturated group-containing monocarboxylic acid (c), Photocurability and alkali developability obtained by reacting acrylate compound (b,) with polybasic acid anhydride (d), but containing different types of aromatic rings regularly and repeatedly As a result, a cured product with high mechanical strength can be obtained, and a linear structure can provide a cured product with high heat resistance, as well as adhesion to substrates, electroless plating resistance, electrical properties, and flexibility. A cured product excellent in moisture absorption resistance, PCT (pressure cook-force) resistance, etc. can be obtained.
OM OM
CH2— CH- •CH2一 0—； '一 0- -CH: -CH— CH2一 0— Y' — 0-CH 2 - CH- • CH 2 one 0-; 'single 0- -CH: -CH- CH 2 one 0- Y' - 0-
\ / \ /
0  0
0M  0M
— CH2— CH— CH2— 0— X' — 0- -CHa一 CH— CH2 · · · (5)— CH 2 — CH— CH 2 — 0— X '— 0- -CHa-CH— CH 2 · · · (5)
■ 」 n \ / ■ ”n \ /
0  0
式中、 X' と Y5 は互いに異なる 2価の芳香環を表わし、 . Μはグリシジル 基及び/又は水素原子を表わし、 ηは 1~20の整数を表わす。 In the formula, X ′ and Y 5 represent different divalent aromatic rings,... Represents a glycidyl group and / or a hydrogen atom, and η represents an integer of 1 to 20.
以下、 本発明の活性エネルギー線硬化性樹脂及びこれを用いた光硬化性 - 熱硬化性組成物の各成分について詳細に説明する。 まず、 本発明の活性エネ ルギ一線硬化性樹脂について説明する。  Hereinafter, each component of the active energy ray-curable resin of the present invention and the photocurable-thermosetting composition using the same will be described in detail. First, the active energy linear curable resin of the present invention will be described.
前記一般式 （5) で示される多核エポキシ化合物 （a5 ) は、 二官能芳香 '族エポキシ化合物と二官能芳香族アルコールとを原料として、 前述したよう に、 公知のェ一テル化触媒を用い、 溶媒中又は無溶媒下、 交互に重合させ、 得られたアルコ一ル性の二級の水酸基にェビハ口ヒドリンを、 ジメチルスル ホキシド、 N, N—ジメチルホルムアミ ド、 N, N—ジメチルァセ トアミ ド 等の非プロトン性極性溶媒、 トルエン、 キシレン等の芳香族炭化水素類等の 公知の溶媒中、 苛性ソーダ等のアルカリ金属水酸化物の存在下、 反応させて 得られる。 二官能芳香族エポキシ化合物及び二官能芳香族アルコールとして は、 上記活性エネルギ一線硬化性樹脂の合成においては、 先に例示したもの に限定.されるものではないが、 先に例示した二官能芳香族エポキシ化合物及 び二官能芳香族アルコールを用いることが好ましいことは勿論である。 The polynuclear epoxy compound (a 5 ) represented by the general formula (5) is a bifunctional aromatic compound. As described above, the alcoholic property obtained by alternately polymerizing a group III epoxy compound and a bifunctional aromatic alcohol as raw materials in a solvent or in the absence of a solvent using a known etherification catalyst as described above. To the secondary hydroxyl group, known hydrin hydrin is used, aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene. In the presence of an alkali metal hydroxide such as caustic soda. In the synthesis of the active energy linear curable resin, the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol are not limited to those exemplified above, but may be any of the bifunctional aromatic epoxy compounds exemplified above. Of course, it is preferable to use an epoxy compound and a bifunctional aromatic alcohol.
次に、 前記一般式 （5) で示される多核エポキシ化合物 （a' ) に不飽和 基含有モノカルボン酸を、 前述したように、 有機溶剤の存在下あるいは非存 在下で、 ハイ ドロキノンや酸素などの重合禁止剤、 及びトリェチルァミン等 の三級アミン、 トリエチルペンジルアンモニゥムクロライ ド等の四級アンモ ニゥム塩、 2—ェチルー 4ーメチルイミダゾール等のイミダゾール化合物、 トリフエニルホスフィン等のリン化合物などの反応触媒の共存下、 通常約 8 0〜 1 30。Cで反応させることにより、 多核エポキシァクリレート化合物 (b5 ) が得られる。 Next, an unsaturated group-containing monocarboxylic acid is added to the polynuclear epoxy compound (a ′) represented by the general formula (5) in the presence or absence of an organic solvent, as described above, for example, in the presence of hydroquinone or oxygen. Polymerization inhibitors, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylpentyl ammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine. Usually about 80 to 130 in the presence of a reaction catalyst. By reacting with C, a polynuclear epoxy acrylate compound (b 5 ) is obtained.
上記反応により生成したエポキシァクリレート化合物 （b， ) のアルコ一 ル性水酸基に多塩基酸無水物 （d) を反応させることにより本発明の活性ェ ネルギ一線硬化性樹脂 （A) が得られるが、 この反応において、 多塩基酸無 水物 （d) の使用量は、 上記反応生成物中のアルコール性水酸基に対して無 水物基が 99 ： 1〜 1 ： 99の割合が適しており、 50〜200mgKOH /g、 好ましくは 50〜 120mgKOH/gの範囲内にある酸価を有する ことが望ましい。 活性エネルギー線硬化性樹脂 （A) の酸価が 50mgKO H/gよりも低いときは、 アルカリ水溶液に対する溶解性が悪くなり、 形成 した塗膜の現像が困難になる。 一方、 200 mgKOH/gよりも高くなる と、露光の条件によらず露光部の表面まで現像されてしまい、好ましくない。 反応は、 前述した有機溶剤の存在下又は非存在下でハイ ドロキノンゃ酸素 等の重合禁止剤の存在下、 通常約 5 0 - 1 3 0 °Cで行なう。 このとき必要に 応じて、 ト リェチルァミン等の三級ァミン、 ト リェチルベンジルアンモニゥ ムクロライ ド等の四級アンモニゥム塩、 2 —ェチル— 4 —メチルイ ミダゾー ル等のイ ミダゾ一ル化合物、 ト リフエニルホスフィ ン等のリン化合物等を触 媒として添加してもよい。 The activated energy linear curable resin (A) of the present invention is obtained by reacting a polybasic acid anhydride (d) with the alcoholic hydroxyl group of the epoxy acrylate compound (b,) produced by the above reaction. However, in this reaction, a suitable amount of the polybasic acid anhydride (d) is a ratio of the anhydride group to the alcoholic hydroxyl group in the above reaction product of 99: 1 to 1:99. It is desirable to have an acid number in the range of 50-200 mg KOH / g, preferably 50-120 mg KOH / g. When the acid value of the active energy ray-curable resin (A) is lower than 50 mg KOH / g, the solubility in an alkaline aqueous solution becomes poor, and the development of the formed coating film becomes difficult. On the other hand, if it is higher than 200 mgKOH / g, the surface of the exposed portion is developed irrespective of the exposure conditions, which is not preferable. The reaction is carried out in the presence or absence of the above-mentioned organic solvent and in the presence of a polymerization inhibitor such as hydroquinone-oxygen, usually at about 50 to 130 ° C. At this time, if necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazol, and triphenyl. A phosphorus compound such as phosphine may be added as a catalyst.
上記多塩基酸無水物 （ d ) としては、 メチルテトラヒ ドロ無水フ夕ル酸、 テ トラヒ ドロ無水フ夕ル酸、 へキサヒ ドロ無水フ夕ル酸、 メチルへキサヒ ド 口無水フ夕ル酸、 無水ナジック酸、 3 , 6—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、 テ トラブロ モ無水フ夕ル酸等の脂環式二塩基酸無水物；無水コハク酸、 無水マレィン酸、 無水ィタコン酸、 ォクテニル無水コハク酸、 ペン夕 ドデセニル無水コハク酸、 無水フ夕ル酸、 無水ト リメ リ ッ ト酸等の脂肪族又は芳香族二塩基酸無水物、 あるいはビフエ二ルテトラカルボン酸二無水物、 ジフエニルエーテルテ トラ カルボン酸二無水物、 ブタンテ トラカルボン酸二無水物、 シクロペン夕ンテ トラカルボン酸二無水物、 無水ピロメ リ ッ ト酸、 ベンゾフヱノンテ トラカル ボン酸二無水物等の脂肪族又は芳香族四塩基酸二無水物が挙げられ、 これら の 1種又は 2種以上を使用することができる。 これらの中でも、 脂環式二塩 基酸無水物が特に好ましい。  Examples of the above polybasic acid anhydrides (d) include methyltetrahydrofluoric anhydride, tetrahydrofluoric anhydride, hexahydrofluoric anhydride, methylhexahydrofuran anhydride, and anhydrous anhydride. Alicyclic dibasic anhydrides such as nadic acid, 3,6-endmethylenetetrahydroanhydrophthalic acid, methylendmethylenetetrahydrophthalic anhydride, tetrabromobromoanhydride; succinic anhydride; Aliphatic or aromatic dibasic anhydrides such as maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, fumaric anhydride, trimellitic anhydride, etc., or biphenyl Tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tricarboxylic dianhydride, cyclopentene tetracarboxylic dianhydride, anhydrous Lome Li Tsu preparative acid include aliphatic or aromatic tetracarboxylic acid dianhydride such as Benzofuwenonte Torakaru Bonn dianhydride, it can be used one or two or more of these. Of these, alicyclic dibasic acid anhydrides are particularly preferred.
本発明の活性エネルギー線硬化性樹脂 （A ) の数平均分子量は、 4 0 0〜 1 0 , 0 0 0、 好ましくは 5 0 0〜 7 , 0 0 0、 より好ましくは 5 0 0〜 3 , 0 0 0である。 活性エネルギー線硬化性樹脂の数平均分子量が 4 0 0未満で は、 得られる硬化物の強靱性が充分でなく、 一方、 1 0， 0 0 0を超えると 溶媒に対する溶解性が低下するので好ましくない。  The number average molecular weight of the active energy ray-curable resin (A) of the present invention is 400 to 100,000, preferably 500 to 7,000, more preferably 500 to 3, 0 0 0. When the number average molecular weight of the active energy ray-curable resin is less than 400, the toughness of the obtained cured product is not sufficient. On the other hand, when it exceeds 100,000, the solubility in a solvent is reduced, so that it is preferable. Absent.
本発明のアル力リ現像可能な光硬化性 ·熱硬化性樹脂組成物は、 前記活性 エネルギー線硬化性樹脂 （A ) に加えて、 感光性 （メタ） ァクリ レート化合 物 （B ) として、 1分子中に 1個以上の （メタ） ァクリロイルォキシ基を有 する室温で液体、 固体又は半固形の感光性 （メタ） ァクリ レート化合物が含 有できる。 これら感光性 （メタ） ァクリレート化合物の使用目的は、 組成物 の光反応性を上げることにある。 室温で液状の感光性 （メタ） ァクリレ一ト 化合物は、 組成物の光反応性を上げる目的の他、 組成物を各種の塗布方法に 適した粘度に調整したり、アル力リ水溶液への溶解性を助ける役割も果たす。 しかし、 室温で液状の感光性 （メタ） ァクリレート化合物を多量に使用する と、 形成される塗膜の指触乾燥性が得られず、 また塗膜の特性も悪化する傾 向があるので、 多量に使用することは好ましくない。 感光性 （メタ） ァクリ レート化合物 （B ) の配合量は、 前記活性エネルギー線硬化性樹脂 （A ) 1 0 0質量部 （固形分として、 以下同様） に対して 1 0〜 6 0質量部、 好まし くは 1 5〜 5 0質量部の割合が望ましい。 The photo-curable and thermo-curable resin composition of the present invention, which is capable of being fully developed, comprises a photosensitive (meth) acrylate compound (B) in addition to the active energy ray-curable resin (A). Contains a liquid, solid or semi-solid photosensitive (meth) acrylate compound at room temperature having one or more (meth) acryloyloxy groups in the molecule. Yes you can. The purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the composition. Photosensitive (meth) acrylate compounds that are liquid at room temperature are used to increase the photoreactivity of the composition, adjust the composition to a viscosity suitable for various coating methods, and dissolve it in aqueous solutions. It also plays a role in helping sex. However, if a large amount of a photosensitive (meth) acrylate compound that is liquid at room temperature is used in a large amount, the formed coating film cannot be dried to the touch, and the characteristics of the coating film tend to deteriorate. Is not preferred. The amount of the photosensitive (meth) acrylate compound (B) is 10 to 60 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin (A) (the same hereinafter as solid content), Preferably, the proportion is 15 to 50 parts by mass.
上記感光性 （メタ） ァクリレート化合物 （B ) としては、 例えば、 2—ヒ ドロキシェチルァクリレート、 2—ヒ ドロキシプロビルァクリレート、 ペン 夕エリスリ トールト リァクリレート、 ジペン夕エリスリ ト一ルペン夕ァクリ レートなどの水酸基含有のァクリレート類； ポリエチレングリコ一ルジァク リレート、 ポリプロピレングリコ一ルジァクリレートなどの水溶性のァクリ レート類； トリメチロールプロパン トリァクリ レート、 ペン夕エリスリ ト一 ルテトラァクリ レート、 ジペン夕エリスリ トールへキサァクリレートなどの 多官能アルコールの多官能ポリエステルァクリレート類； ト リメチ口一ルプ 口パン、 水添ビスフエノ一ル A等の多官能アルコールもしくはビスフエノ一 ル 、 ビフエノールなどの多官能フエノールのエチレンオキサイ ド付加物、 プロピレンォキサイ ド付加物のァクリレート類； 上記水酸基含有ァクリレ一 トのィソシァネート変成物である多官能もしくは単官能ポリウレタンァク リ レート ； ビスフエノール Aジグリシジルエーテル、 水添ビスフエノール Aジ グリシジルエーテル又はフエノールノボラックエポキシ樹脂の （メタ） ァク リル酸付加物であるエポキシァクリ レート類、 及び上記ァクリレート類に対 応するメタクリ レート類などが挙げられ、 これらは単独で又は 2種以上を組 み合わせて使用することができる。 これらの中でも、 1分子中に 2個以上の (メタ） ァクリロイルォキシ基を有する多官能 （メタ） ァクリレート化合物 が好ましい。 Examples of the photosensitive (meth) acrylate compound (B) include 2-hydroxyhexyl acrylate, 2-hydroxypropyl acrylate, pen erythritol triacrylate, and diphenyl erythritol triacrylate. Water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentyl erythritol hexaacrylate, and the like. Polyfunctional polyester acrylates of polyfunctional alcohols; Trimethyl lip-to-mouth buns, polyfunctional alcohols such as hydrogenated bisphenol A or polyfunctional phenols such as bisphenol and biphenol Acrylates of ethylene oxide adducts and propylene oxide adducts of the above; polyfunctional or monofunctional polyurethane acrylates as isocyanate modified products of the above-mentioned hydroxyl group-containing acrylates; bisphenol A diglycidyl ether; hydrogenated Epoxy acrylates, which are (meth) acrylic acid adducts of bisphenol A diglycidyl ether or phenol novolak epoxy resin, and methacrylates corresponding to the above acrylates, may be used alone or in combination of two or more. The above can be used in combination. Among them, polyfunctional (meth) acrylate compounds having two or more (meth) acryloyloxy groups in one molecule Is preferred.
前記光重合開始剤 （ C ) としては、 例えば、 ペンゾイン、 ベンゾインメチ ルェ一テル、 ペンゾインェチルエーテル、 ベンゾインイソプロピルエーテル 等のベンゾインとベンゾインアルキルェ一テル類； ァセ トフエノン、 2 , 2 —ジメ トキシー 2—フエニルァセ トフエノン、 2， 2—ジェトキシー 2—フ ェニルァセ トフエノン、 1， 1ージクロロアセ トフエノン等のァセ トフエノ ン類 ； 2—メチル一 1— [ 4— (メチルチオ） フエニル] — 2—モルホリノ ァミノプロパノン一 1、 2—ベンジル一 2—ジメチルァミノ一 1— ( 4—モ ルホリノフエニル） 一ブタン一 1一オン、 N , N—ジメチルアミノアセ トフ ェノン等のアミノアセ トフエノン類； 2—メチルアントラキノン、 2—ェチ ルアントラキノン、 2— t—ブチルアントラキノン、 1—クロ口アン トラキ ノン等のアントラキノン類； 2， 4一ジメチルチオキサントン、 2 , 4—ジ ェチルチオキサン トン、 2—クロ口チォキサン トン、 2 , 4—ジイソプロピ ルチオキサントン等のチォキサントン類；ァセ トフエノンジメチルケ夕一ル、 ベンジルジメチルケ夕一ル等のケ夕一ル類 ； ベンゾィルパ一ォキシ ド、 クメ ンバーオキシド等の有機過酸化物 ； 2 , 4 , 5— ト リアリールイ ミダゾ一ル 二量体、 リボフラビンテトラブチレ一ト、 2—メルカプトべンゾイ ミダゾ一 ル、 2—メルカプトベンゾォキサゾ一ル、 2—メルカプトべンゾチアゾール 等のチォ一ル化合物 ； 2 , 4 , 6— トリス— s— ト リァジン、 2 , 2 , 2 - ト リブロモエタノール、 ト リブロモメチルフエニルスルホン等の有機ハロゲ ン化合物；ペンゾフエノン、 4 , 4 ' ―ビスジェチルァミノべンゾフエノン 等のペンゾフエノン類又はキサントン類； 2， 4 , 6— ト リメチルベンゾィ ルジフエニルホスフィ ンォキサイ ドなどが挙げられる。  Examples of the photopolymerization initiator (C) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2, 2 — Acetophenones such as dimethoxy-2-phenylacetophenone, 2,2-ethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] —2-morpholinoaminopropanone 1,2-Benzyl-1-dimethylamino-1- (4-morpholinophenyl) 1-butane-11-one, aminoacetophenones such as N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethyl Luanthraquinone, 2-t-butylanthraquinone, 1-chloro Anthraquinones such as anthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetatephenone dimethyl ketone Kerosenes such as benzyldimethyl ketone; organic peroxides such as benzoyl peroxide and cumene oxide; 2,4,5-triarylimidazole dimer and riboflavin tetrabutylene Thiol compounds such as 1-, 2-mercaptobenzoylmidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine; 2,2 Organohalogen compounds such as 2,2-tribromoethanol and tribromomethylphenylsulfone; benzophenone, 4,4'-bisje Penzofuenon acids or xanthones such as Ruamino base Nzofuenon; 2, 4, such as 6 preparative Rimechirubenzoi Le diphenyl phosphide Nokisai de like.
これら公知慣用の光重合開始剤は、 単独で又は 2種類以上の混合物として 使用でき、 さらには N , N—ジメチルァミノ安息香酸ェチルエステル、 N , N—ジメチルアミノ安息香酸ィソァミルエステル、 ペンチルー 4ージメチル ァミノべンゾエート、 ト リェチルァミン、 ト リエタノールァミン等の三級ァ ミン類などの光開始助剤を加えることができる。 また可視光領域に吸収のあ る C G I— 784等 （チパ ' · スペシャルティ ' ケミカルズ社製） のチタノセ ン化合物等も、 光反応を促進するために添加することもできる。 特に好まし い光重合開始剤は、 2—メチル— 1一 [4一 （メチルチオ） フエニル] 一 2 —モルホリノアミノプロパノン一 1、 2—ベンジル一 2—ジメチルアミノー 1— ( 4—モルホリノフエニル） 一ブタン一 1一オン等であるが、 特にこれ らに限られるものではなく、 紫外光もしくは可視光領域で光を吸収し、 （メ 夕） ァクリロイル基等の不飽和基をラジカル重合させるものであれば、 光重 合開始剤、 光開始助剤に限らず、 単独であるいは複数併用して使用できる。 前記光重合開始剤の使用量（光開始助剤を用いる場合にはこれらの合計量） は、 前記活性エネルギー線硬化性樹脂 （A) 1 00質量部に対して 0. 1〜 25質'量部、 好ましくは 0. 5〜 20質量部の割合が望ましい。 光重合開始 剤の配合量が上記範囲よりも少ない場合、 活性エネルギー線の照射を行なつ ても硬化しないか、 もしくは照射時間を増やす必要があり、 適切な塗膜物性 が得られ難くなる。一方、 上記範囲よりも多量に光重合開始剤を添加しても、 光硬化性に変化は無く、 経済的に好ましくない。 These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylamino Photoinitiating aids such as tertiary amines such as benzoate, triethylamine and triethanolamine can be added. In addition, absorption in the visible light region Titanocene compounds such as CGI-784 (manufactured by Chipa and Specialty Chemicals) can also be added to promote the photoreaction. Particularly preferred photopolymerization initiators are 2-methyl-11- [4- (methylthio) phenyl] -12-morpholinoaminopropanone 1-1,2-benzyl-12-dimethylamino-1- (4-morpholinoff (Enyl) 1-butane-11-one, etc., but not particularly limited thereto. Absorbs light in the ultraviolet or visible light region, and radically polymerizes unsaturated groups such as (meth) acryloyl groups. As long as they are used, they are not limited to the photopolymerization initiator and the photoinitiator, but can be used alone or in combination. The amount of the photopolymerization initiator used (or the total amount thereof when a photoinitiator is used) is 0.1 to 25 mass% based on 100 parts by mass of the active energy ray-curable resin (A). Parts, preferably 0.5 to 20 parts by weight. When the amount of the photopolymerization initiator is less than the above range, the composition does not cure even when irradiated with active energy rays, or the irradiation time needs to be increased, so that it becomes difficult to obtain appropriate coating film properties. On the other hand, even if the photopolymerization initiator is added in a larger amount than the above range, there is no change in photocurability, which is not economically preferable.
また、 本発明の光硬化性 ·熱硬化性組成物は、 前記活性エネルギー線硬化 性樹脂 （A) や感光性 （メタ） ァク リレート化合物 （B) を溶解させ、 また 組成物を塗布方法に適.した粘度に調整するために、 先に例示したような有機 溶剤を単独で又は 2種以上組み合わせて配合することができる。 なお、 有機 溶剤の配合量は、 塗布方法に応じた任意の量とすることができる。  In addition, the photocurable and thermosetting composition of the present invention dissolves the active energy ray-curable resin (A) and the photosensitive (meth) acrylate compound (B). In order to adjust the viscosity to an appropriate level, the organic solvents as exemplified above can be used alone or in combination of two or more. The amount of the organic solvent can be set to any amount according to the application method.
前記多官能エポキシ化合物 （D) としては、 具体的には、 ジャパンェポキ シレジン （株） 製のェピコート 828、 ェピコ一ト 834、 ェピコート 10 0 1、 ェピコート 1 004、 大日本インキ化学工業 （株） 製のェピクロン 8 40、 ェピクロン 850、 ェピクロン 1050、 ェピクロン 205 5、 東都 化成 （株） 製のェポトート YD— 0 1 1、 YD— 0 13、 YD— 127、 Y D— 128、 ダウケミカル社製の D. E. R. 3 17、 D . E . R. 33 1、 D . E. R. 6 6 1 D. E . R . 664、 チバ · スペシャルティ . ケミカ ルズ社製のァラルダイ ド 607 1、 ァラルダイ ド 6084、 ァラルダイ G Y 2 5 0、 ァラルダイ ド GY 2 6 0、 住友化学工業 （株） 製のスミーェポキ シ E SA— 0 1 1、 E S A— 0 14、 E LA— 1 1 5、 E LA— 1 2 8、 旭 化成工業 （株） 製の A. E . R. 3 30、 A. E . R. 3 3 1、 A. E . R. 6 6 1、 A. E . R. 6 64等 （何れも商品名） のビスフエノ一ル A型ェポ キシ樹脂 ； ジャパンエポキシレジン （株） 製のェピコ一ト Y L 9 0 3、 大日 本ィンキ化学工業 （株） 製のェピクロン 1 5 2、 ェピクロン 1 6 5、 東都化 成 （株） 製のェポトート YD B— 400、 YD B— 5 0 0、 ダウケミカル社 製の D. E. . 542、 チバ 'スペシャルティ ' ケミカルズ社製のァラル ダイ ド 8 0 1 1、 住友化学工業 （株） 製のスミ—エポキシ E S B— 4 0 0、 E S B— 70 0、 旭化成工業 （株） 製の A. E . R. 7 1 1、 A. E . R. 7 1 4等 （何れも商品名） のブロム化エポキシ樹脂 ； ジャパンエポキシレジ ン （株） 製のェピコ一ト 1 5 2、 ェピコート 1 54、 ダウケミカル社製の D . E . N. 43 1、 D . E . N. 43 8、 大日本ィンキ化学工業 （株） 製のェ ピクロン N— 7 3 0、 ェピクロン N— 7 7 0、 ェピクロン N— 8 6 5、 東都 化成 （株） 製のェポトート YD CN— 7 0 1、 YD CN— 7 04、 チバ ' ス ぺシャルティ ' ケミカルズ社製のァラルダイ ド E CN 1 2 3 5、 ァラルダイ ド E CN 1 2 7 3、 ァラルダイ ド E CN 1 2 9 9、 ァラルダイ ド XP Y 3 0 7、 日本化薬 （株） 製の E P PN— 20 1、 E O CN— 1 0 2 5、 E O CN — 1 0 2 0 , E O CN— 1 04 S、 RE— 3' 0 6、 住友化学工業 （株） 製の スミ—エポキシ E S CN— 1 9 5 X、 E S CN— 2 2 0、 旭化成工業 （株） 製の A. E . R. E CN_ 2 3 5、 E CN— 2 9 9等 （何れも商品名） のノ ボラヅク型ェ'ポキシ樹脂；大日本ィンキ化学工業 （株） 製のェピクロン 8 3 0、 ジャパンエポキシレジン （株） 製のェピコ一ト 8 0 7、 東都化成 （株） 製のェポトート YD F— 1 7 0、 YD F— 1 7 5、 YD F— 2 0 04、チバ · スペシャルティ ' ケミカルズ社製のァラルダイ ド XPY 3 0 6等 （何れも商 品名） のビスフエノ一ル F型エポキシ樹脂；東都化成 （株） 製のェポトート S T— 2 004、 S T— 2 0 0 7、 S T— 3 0 0 0 (商品名） 等の水添ビス フエノール A型エポキシ樹脂； ジャパンエポキシレジン （株） 製のェピコ一 ト 6 04、 東都化成 （株） 製のェポトート YH— 434、 チバ ' スペシャル ティ · ケミカルズ社製のァラルダイ ド MY 7 2 0、 住友化学工業 （株） 製の スミ—エポキシ E LM— 1 2 0等 （何れも商品名） のグリシジルアミン型ェ ポキシ樹脂； チバ · スペシャルティ 'ケミカルズ社製のァラルダイ ド C Y— 3 5 0 (商品名） 等のヒダントイン型エポキシ樹脂；ダイセル化学工業 （株） 製のセロキサイ ド 2 0 2 1、 チバ · スペシャルティ . ケミカルズ社製のァラ ルダイ ド CY 1 7 5、 CY 1 7 9等（何れも商品名）の脂環式エポキシ樹脂 ； ジャパンエポキシレジン （株） 製の YL— 9 3 3、 ダウケミカル社製の T . E . N. 、 E P PN- 5 0 1, E P PN— 5 0 2等 （何れも商品名） のト リ ヒ ドロキシフエニルメタン型エポキシ樹脂； ジャパンエポキシレジン （株） 製の YL— 6 0 5 6、 YX— 4 0 0 0、 Y L - 6 1 2 1 (何れも商品名） 等 のビキシレノール型もしくはビフエノール型エポキシ樹脂又はそれらの混合 物； 日本化薬 （株） 製 E B P S— 2 00、 旭電化工業 （株） 製 E PX— 3 0、 大日本ィンキ化学工業 （株） 製の EX A— 1 5 1 4 (商品名） 等のビスフエ ノ一ル S型エポキシ樹脂 ； ジャパンエポキシレジン （株） 製のェピコ一ト 1 5 7 S (商品名） 等のビスフエノール Aノボラック型エポキシ樹脂 ； ジャパ ンエポキシレジン （株） 製のェピコ一ト YL— 9 3 1、 チバ 'スペシャルテ ィ · ケミカルズ社製のァラルダイ ド 1 63等 （何れも商品名） のテ トラフエ 二ロールエタン型エポキシ樹脂； チバ · スペシャルティ ' ケミカルズ社製の ァラルダイ ド P T 8 1 0、 日産化学工業 （株） 製の T E P I C等 （何れも商 品名） の複素璟式エポキシ樹脂 ； 日本油脂 （株） 製プレンマー D GT等のジ グリシジルフ夕レート樹脂；東都化成 （株） 製 Z X— 1 0 6 3等のテ トラグ リシジルキシレノィルェタン樹脂 ；新日鉄化学 （株） 製 E SN- 1 9 0、 E S N— 3 6 0、 大日本ィンキ化学工業 （株） 製 HP— 40 3 2、 EXA- 4 7 5 0、 EXA— 47 0 0等のナフ夕レン基含有エポキシ樹脂；大日本イン キ化学工業 （株） 製 HP— 7 2 0 0、 HP— 7 2 0 0 H等のジシクロペン夕 ジェン骨格を有するエポキシ樹脂 ； 日本油脂 （株） 製 C P— 5 0 S、 CP— 5 0 M等のグリシジルメ夕ァクリ レート共重合系エポキシ樹脂； さらにシク 口へキシルマレイ ミ ドとグリシジルメタァクリレートの共重合エポキシ樹脂 等が挙げられるが、 これらに限られるものではない。 これらエポキシ樹脂は 単独で又は 2種以上を用いることができる。 これらの中でも特にビフエノ一 ル型もしくはビキシレノ一ル型エポキシ樹脂又はそれらの混合物が好まし く、 他のエポキシ樹脂を用いる場合においても、 組成物中に前記活性エネル ギ一線硬化性樹脂 （A) 1 0 0質量部当り 5質量部以上の割合で含まれてい ることが好ましい。 Specific examples of the polyfunctional epoxy compound (D) include Epikote 828, Epikoto 834, Epikote 101, Epikote 1004, manufactured by Japan Epoxy Resin Co., Ltd., and Dainippon Ink and Chemicals, Inc. Epicron 840, Epicron 850, Epicron 1050, Epicron 205 5, Epotote YD-011, YD-013, YD-013, YD-127, YD-128 manufactured by Toto Kasei, DER 317 manufactured by Dow Chemical D.E.R. 331, D.ER 661 D.E.R. 664, Ciba Specialty Chemicals, Inc. Araldide 6071, Araldide 6084, Araldie G Y250, Araldide GY260, Sumie-poxy ESA—011, ESA—014, ELA—115, ELA—128, Sumitomo Chemical Co., Ltd., Asahi Kasei A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664, etc. manufactured by Kogyo Co., Ltd. (all are trade names) Bisphenol A-type epoxy resin; Epoxy YL 903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152, Epiclon 165 manufactured by Dainichi Ink Chemical Industry Co., Ltd. Yepototo YD B-400, YD B-500, manufactured by SEI Co., Ltd., DE.542, manufactured by Dow Chemical Co., Ltd., Aral Dide 801, manufactured by Ciba 'Specialty' Chemicals Co., Ltd., Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESB-400, ESB-700, manufactured by Asahi Kasei Kogyo Co., Ltd. A.E.R.711, A.E.R.711.4 (all trade names) Brominated epoxy resin; Japan Epoxy Resin Co., Ltd. 152, Epikote 154, D.E.N. 431, D.E.N. 438, Dow Chemical Co., Ltd., Epicron N—, manufactured by Dainippon Ink & Chemicals, Inc. 730, Epiclone N—770, Epiclone N—865, Yeptoto YD CN—701, YD CN—704, manufactured by Toto Kasei Co., Ltd., Araldai manufactured by Ciba's Specialty Co., Ltd. E CN 1 2 3 5, Araldide E CN 1 2 7 3, Araldide E CN 1 2 9 9, Araldide XP Y 3 0 7, Nippon Kayaku Co., Ltd. EP PN—201, EO CN — 10 25, EO CN — 10 20, EO CN— 104 S, RE— 3 '06, Sumitomo Chemical Industries, Ltd. Sumi—Epoxy ES CN— 195 X, ES CN— 220, Novolak-type epoxy resin of A.E.R. ECN_235, ECN—299, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd .; Epiclon 830, manufactured by Japan Epoxy Co., Ltd. Epikoto 807 manufactured by Resin Co., Ltd., Epototo YD F—170, YD F—175, YD F—2004 manufactured by Toto Kasei Co., Ltd., manufactured by Ciba Specialty Chemicals Bisphenol F-type epoxy resin such as Araldide XPY306 (all trade names); EP-TOTO ST-2004, ST-200, ST-300 (manufactured by Toto Kasei Co., Ltd.) Nippon Epoxy Resin Co., Ltd. 604, Epotote YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba's Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Glycidylamine-type epoxy resins (all trade names); Hydantoin-type epoxy resins such as Ciba Specialty's Araldide CY-350 (trade name) manufactured by Chemicals; Celloxide manufactured by Daicel Chemical Industries, Ltd. Alicyclic epoxy resins such as CY175 and CY179 (all trade names) manufactured by Chemicals, Inc .; YL- manufactured by Japan Epoxy Resin Co., Ltd. 933, Dow Chemical's T.E.N., EP PN-501, EP PN-502, etc. (each a trade name) trihydroxyphenyl methane type epoxy resin; Japan Epoxy YL—605 manufactured by Resin Co., Ltd. 6, YX-400, YL-6121 (all trade names) and other bixylenol-type or biphenol-type epoxy resins or mixtures thereof; Nippon Kayaku Co., Ltd. EBPS-200, Asahi Bisphenol S-type epoxy resin such as E PX-30 manufactured by Denka Kogyo Co., Ltd. and EX A-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc .; Japan Epoxy Resin Co., Ltd. Bisphenol A novolak type epoxy resin such as Epoxy® 15 S (trade name); Epoxy® YL-931, manufactured by Japan Epoxy Resin Co., Ltd., manufactured by Ciba's Specialty Chemicals Tetrafue two-roll ethane epoxy resin such as Araldide 163 (all trade names); Ciba Specialty's Araldide PT810 manufactured by Chemicals, TEPIC manufactured by Nissan Chemical Industry Co., Ltd. Product name) Complex epoxy Resin: Diglycidyl phosphate resin such as Plemmer D GT manufactured by Nippon Yushi Co., Ltd .; Tetraglycidyl xylenylethane resin such as ZX-1063 manufactured by Toto Kasei Co., Ltd .; Nippon Steel Chemical Co., Ltd. Epoxy resin containing naphthylene group such as ESN-190, ESN-360, Dainippon Ink & Chemicals, Inc. HP-4032, EXA-470, EXA-4700; Epoxy resins having a dicyclopentene skeleton such as HP-720 and HP-720H manufactured by Dainippon Ink and Chemicals, Inc .; CP-50S, CP-5 manufactured by NOF Corporation Glycidyl methacrylate copolymer epoxy resin such as 0 M; Examples include, but are not limited to, copolymerized epoxy resins of hexyl maleimide and glycidyl methacrylate. These epoxy resins can be used alone or in combination of two or more. Among these, a biphenol-type or bixylenol-type epoxy resin or a mixture thereof is particularly preferable. Even when another epoxy resin is used, the active energy linear curable resin (A) 1 It is preferably contained in a proportion of 5 parts by mass or more per 100 parts by mass.
上記のような多官能エポキシ化合物 （D) は、 熱硬化することにより、 ソ ルダーレジス トの密着性、 耐熱性等の特性を向上させる。 その配合量は、 前 記活性エネルギー線硬化性樹脂（A) 1 0 0質量部に対して 1 0質量部以上、 1 00質量部以下で充分であり、好ましくは 2 5 - 6 0質量部の割合である。 多官能エポキシ化合物 （D) の配合量が 1 0質量部未満の場合、 硬化皮膜の 吸湿性が高くなつて P C T耐性が低下し易くなり、 また、 はんだ耐熱性ゃ耐 無電解めつき性も低くなり易い。 一方、 1 0 0質量部を超えると、 塗膜の現 像性や硬化皮膜の耐無電解めつき性が悪くなり、 また P C T耐性も劣ったも のとなる。  The above-mentioned polyfunctional epoxy compound (D) improves properties such as adhesiveness and heat resistance of the solder resist by heat curing. The compounding amount is sufficient in the range of 100 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable resin (A), and preferably 25 to 60 parts by mass. Percentage. If the amount of the polyfunctional epoxy compound (D) is less than 10 parts by mass, the PCT resistance tends to decrease due to the high hygroscopicity of the cured film, and the solder heat resistance and the electroless plating resistance are also low. Easy to be. On the other hand, if it exceeds 100 parts by mass, the imageability of the coating film and the electroless plating resistance of the cured film will be poor, and the PCT resistance will also be poor.
前記硬化触媒 （E) としては、 例えば、 イ ミダゾ一ル、 2—メチルイ ミダ ゾール、 2—ェチルイ ミダゾ一ル、 2—ェチルー 4—メチルイ ミダゾール、 2—フエ二ルイ ミダゾ一ル、 4—フエ二ルイ ミダゾ一ル、 1ーシァノエチル — 2—フエ二ルイ ミダゾ一ル、 1一 （2—シァノエチル） 一 2—ェチル一4 一メチルイミダゾ一ル等のイ ミダゾール誘導体； ジシアンジアミ ド、 ベンジ ルジメチルァミン、 4一 （ジメチルァミノ） 一 N, N—ジメチルベンジルァ ミン、 4—メ トキシー N, N—ジメチルベンジルァミン、 4—メチル一 N, N—ジメチルベンジルァミン等のアミン化合物、 アジビン酸ヒ ドラジド、 セ パシン酸ヒ ドラジド等のヒ ドラジン化合物 ； ト リフエニルホスフィ ン等のリ ン化合物など、 また市販されているものとしては、 例えば四国化成 （株） 製 の 2 MZ— A、 2 MZ - OK、 2 Ρ ΗΖ、 2 Ρ 4 ΒΗ Ζ、 2 Ρ 4 ΜΗ Ζ (い ずれもィ ミダゾール系化合物の商品名） 、 サンァプロ社製の U— CAT 3 5 0 3 X、 U— CAT 3 5 0 2 X (いずれもジメチルァミンのブロックイソシ ァネート化合物の商品名） 、 D BU、 DBN、 U- CAT SA 1 0 2s U— CAT 5 002 (いずれも二環式アミジン化合物及びその塩） などが挙げら れる。 特に、 これらに限られるものではなく、 エポキシ樹脂の硬化触媒、 も しくはエポキシ基とカルボキシル基の反応を促進するものであればよく、 単 独で又は 2種以上を混合して使用してもかまわない。 また、 密着性付与剤と しても機能するグアナミン、 ァセ トグアナミン、 ベンゾグアナミン、 メラミ ン、 2 , 4—ジァミノ一 6—メタクリロイルォキシェチルー S— ト リアジン、 2—ビニルー 2 , 4—ジァミノ一 S—ト リアジン、 2—ビニルー 4， 6—ジ アミノー S— ト リアジン ' イソシァヌル酸付加物、 2， 4—ジァミノー 6— メタクリロイルォキシェチルー S— トリアジン · イソシァヌル酸付加物等の S— ト リアジン誘導体を用いることもでき、 好ましくはこれら密着性付与剤 としても機能する化合物を前記硬化触媒と併用する。 上記硬化触媒の配合量 は通常の量的割合で充分であり、 例えば前記活性エネルギー線硬化性樹脂 (A) 1 00質量部に対して 0. ：!〜 2 0質量部、 好ましくは 0. 5〜： 1 5. 0質量部の割合である。 Examples of the curing catalyst (E) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenylimidazole. Imidazole derivatives such as Louis Midazole, 1-Cyanoethyl — 2-phenylmidazole, 1-1 (2-Cyanoethyl) 1-2-ethyl-14-methylimidazole; Dicyandiamide, Benzyldimethylamine, 4- ( Amine compounds such as dimethylamino) 1 N, N-dimethylbenzylamine, 4-methoxy N, N-dimethylbenzylamine, 4-methyl-1-N, N-dimethylbenzylamine, adivic hydrazide, sebacic acid Examples of hydrazine compounds such as hydrazide; phosphorus compounds such as triphenylphosphine; 2MZ-A, 2MZ-OK, 2Ρ4, 2Ρ4ΒΗ, 2 24ΜΗΜΗ (both are trade names of imidazole compounds) manufactured by Kokusei Chemicals Co., Ltd. — CAT 3 5 0 3 X, U— CAT 350 2 X (all are trade names of dimethylamine block isocyanate compounds), DBU, DBN, U-CAT SA 102 s U— CAT 5 002 (all are bicyclic Amidine compounds and salts thereof). In particular, the present invention is not limited to these, and any curing catalyst for an epoxy resin or any catalyst that promotes the reaction between an epoxy group and a carboxyl group may be used. I don't care. Also, guanamine, acetate guanamine, benzoguanamine, melamine, 2,4-diamino-1 6-methacryloyloxetyl-S-triazine, 2-vinyl-2,4-diamino-1 also function as an adhesion promoter. S-triazine such as S-triazine, 2-vinyl-4,6-diamino-S-triazine 'isocyanuric acid adduct, 2,4-diaminol 6-methacryloyloxetyl-S-triazine and isocyanuric acid adduct Derivatives can also be used, and preferably a compound that also functions as an adhesion promoter is used in combination with the curing catalyst. The amount of the above-mentioned curing catalyst to be blended in a usual quantitative ratio is sufficient, for example, from 0.5 to 20 parts by mass, preferably from 0.5 to 100 parts by mass of the active energy ray-curable resin (A). ：: 15.0 parts by mass.
本発明の光硬化性 ·熱硬化性樹脂組成物には、 さらに必要に応じて、 硫酸 バリウム、 チタン酸バリウム、 酸化ケィ素紛、 微粉状酸化ケィ素、 無定形シ リカ、 結晶性シリカ、 溶融シリカ、 球状シリカ、 タルク、 クレー、 炭酸マグ ネシゥム、 炭酸カルシウム、 酸化アルミニウム、 水酸化アルミニウム、 マイ 力等の公知慣用の無機フィ ラーを単独で又は 2種以上配合することができ る。 これらは塗膜の硬化収縮を抑制し、 密着性、 硬度などの特性を向上させ る目的で用いられる。 無機フイラ一の配合量は、 前記活性エネルギ一線硬化 性樹脂 （A) 1 0 0質量部当り 1 0〜3 0 0質量部、 好ましくは 3 0〜2 0 0質量部が適当である。  The photocurable and thermosetting resin composition of the present invention may further include, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely powdered silicon oxide, amorphous silica, crystalline silica, and fused silica. Known or customary inorganic fillers such as silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and myriki can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of a coating film and improving properties such as adhesion and hardness. An appropriate amount of the inorganic filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass, per 100 parts by mass of the active energy linear curable resin (A).
本発明の組成物は、 さらに必要に応じてフタロシアニン · ブルー、 フタ口 シァニン ' グリーン、 アイォジン ' グリーン、 ジスァゾイエロ一、 ク リス夕 ルバイオレッ ト、 酸化チタン、 カーボンブラック、 ナフ夕レンブラックなど の公知慣用の着色剤、 ハイ ドロキノン、ハイ ドロキノンモノメチルエーテル、 tーブチルカテコール、 ピロガロール、 フエノチアジンなどの公知慣用の熱 重合禁止剤、 微粉シリカ、 有機ペントナイ ト、 モンモリロナイ トなどの公知 慣用の増粘剤、 シリコーン系、 フッ素系、 高分子系などの消泡剤及び z又は レペリング剤、 イ ミダゾ一ル系、 チアゾ一ル系、 ト リァゾール系等のシラン 力ップリング剤などのような公知慣用の添加剤類を配合することができる。 以上のような組成を有する本発明の光硬化性 ·熱硬化性樹脂組成物は、 必 要に応じて希釈して塗布方法に適した粘度に調整し、 これを例えば、 回路形 成されたプリント配線板にスクリーン印刷法、 力一テンコート法、 プレーコ —ト法、 ロールコート法等の方法により塗布し、 例えば約 6 0〜 1 0 0 °Cの 温度で組成物中に含まれる有機溶剤を揮発乾燥させることにより、 タックフ リ一の塗膜を形成できる。 その後、 パターンを形成したフォ トマスクを通し て選択的に活性エネルギー線により露光し、 未露光部を希アル力リ水溶液に より現像してレジス トパターンを形成でき、 さらに、 活性エネルギー線の照 射後加熱硬化もしくは加熱硬化後活性エネルギー線の照射、 又は、 加熱硬化 のみで最終硬化 （本硬化） させることにより、 耐熱性、 密着性、 耐無電解め つき性、 電気特性、 フレキシブル性、 耐吸湿性並びに P C T (プレッシャー クヅ力一） 耐性に優れた硬化皮膜 （ソルダ一レジス ト皮膜） が形成される。 上記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 ナト リウム、 炭酸カリウム、 リン酸ナト リウム、 ケィ酸ナトリウム、 アンモ ニァ、 アミン類などのアルカリ水溶液が使用できる。 The composition of the present invention may further contain, if necessary, phthalocyanine blue, lid mouth cyanine 'green', aozin 'green, disazoeello, Chris Leo Violet, titanium oxide, carbon black, Nafurene Black, etc. Known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine; known and commonly used thickeners such as finely divided silica, organic pentonites, and montmorillonite And conventional additives such as silicone-based, fluorine-based, polymer-based antifoaming agents and z- or repelling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, etc. Agents can be blended. The photo-curable and thermo-curable resin composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method. It is applied to the wiring board by screen printing, force coating, plate coating, roll coating, etc., for example, to evaporate the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. By drying, a tack-free coating film can be formed. Thereafter, the resist pattern is selectively exposed to active energy rays through a patterned photomask, and the unexposed portions are developed with a dilute aqueous solution to form a resist pattern. By heat-curing or irradiation with active energy rays after heat-curing, or by final curing (final curing) only by heat-curing, heat resistance, adhesion, electroless plating resistance, electrical properties, flexibility, moisture absorption A cured film (solder-resist film) with excellent properties and PCT (pressure resistance) is formed. As the alkaline aqueous solution, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used.
また、 光硬化させるための照射光源としては、 低圧水銀灯、 中圧水銀灯、 高圧水銀灯、 超高圧水銀灯、 キセノンランプ又はメタルハライ ドランプなど が適当である。 その他、 レーザー光線なども活性エネルギー線として利用で ぎる。  Further, as an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, laser beams can be used as active energy rays.
以下に実施例及び比較例を示して本発明について具体的に説明するが、 以 下の実施例は本発明の例示の目的のためのみのものであり、 本発明を限定す るものではない。 なお、 以下において 「部」 及び 「％」 とあるのは、 特に断 りのない限り全て質量基準である。 Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. However, the following Examples are for the purpose of illustrating the present invention only, and do not limit the present invention. In the following, “parts” and “%” are not particularly noted. All are based on mass unless otherwise noted.
合成例 1  Synthesis example 1
ガス導入管、 攪拌装置、 冷却管及び温度計を備えたフラスコに 1， 5—ジ ヒ ドロキシナフ夕レン 1 69部とエポキシ当量 1 94 g/e q.の 3， 3 5 , 5 ' —テトラメチルー 4， 4 ' —ジヒ ドロキシビフエ二ルジグリシジル ェ一テル 1 1 30部を仕込み、 窒素雰囲気下にて、 攪拌下 1 20°Cで溶解さ せた。 その後、 ト リフエニルホスフィン 0. 65部を添加し、 フラスコ内の 温度を 1 50°Cまで昇温し、 温度を 150°Cに保持しながら、 約 9◦分間反 応させ、 エポキシ当量 402 g/e q. のエポキシ化合物 （ 1 ) を得た。 次 に、 フラスコ内の温度を 70°C以下まで冷却し、 ェピクロルヒ ドリ ン 1 92 2部、 ジメチルスルホキシド 1690部を加え、 攪拌下 70°Cまで昇温し保 持した。 その後、 96 %水酸化ナト リウム 1 14部を 90分間かけて分割添 加した。 添加後、 さら 3時間反応させた。 反応終了後、 過剰のェピクロル ヒ ドリン及びジメチルスルホキシドの大半を 120 °C、 50 mmH gの減圧 下にて蒸留し、 副生塩とジメチルスルホキシドを含む反応生成物をメチルイ ソブチルケトンに溶解させ水洗した。 その後、 油層よりメチルイソプチルケ トンを蒸留回収して、 エポキシ当量 304 g/e q. の多核エポキシ化合物 (a— 1) を得た。 得られた多核エポキシ化合物 （a— 1) は、 エポキシ当 量から計算すると、 前記一般式 （7 a) におけるアルコール性水酸基 1. 7 6個のうち 0. 79個がエポキシ化されている。 従って、 アルコール性水酸 基のエポキシ化率は 45 %である。  In a flask equipped with a gas inlet tube, a stirrer, a condenser tube and a thermometer, 1,69 parts of 1,5-dihydroxynaphthylene and 3,35,5'-epoxy equivalent of 194 g / eq. 3,35,5'-tetramethyl-4 , 4'-Dihydroxybiphenyldiglycidyl ether (110 parts) was charged and dissolved at 120 ° C under stirring in a nitrogen atmosphere. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the reaction was carried out for about 9◦ minutes while maintaining the temperature at 150 ° C, and the epoxy equivalent was 402 g. / e q. epoxy compound (1) was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, 192 parts of epichlorohydrin and 1690 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and maintained. Thereafter, 114 parts of 96% sodium hydroxide was dividedly added over 90 minutes. After the addition, the reaction was further performed for 3 hours. After completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were distilled at 120 ° C. under a reduced pressure of 50 mmHg, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain a polynuclear epoxy compound (a-1) having an epoxy equivalent of 304 g / eq. When the obtained polynuclear epoxy compound (a-1) was calculated from the epoxy equivalent, 0.79 of the 1.76 alcoholic hydroxyl groups in the general formula (7a) were epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 45%.
合成例 2  Synthesis example 2
ガス導入管、 攪拌装置、 冷却管及び温度計を備えたフラスコに 1， 5—ジ ヒ ドロキシナフ夕レン 232部とエポキシ当量 1 94 g/e q . の 3, 3 ' , 5 , 5 ' ―テトラメチル一 4, 4 ' ―ジヒ ドロキシビフエ二ルジグリシジル エーテル 1067部を仕込み、 窒素雰囲気下にて、 攪拌下 120°Cで溶解さ せた。 その後、 ト リフエニルホスフィン 0. 6 5部を添加し、 フラスコ内の 温度を 1 50°Cまで昇温し、 温度を 150°Cに保持しながら、 約 90分間反 応させ、 エポキシ当量 544 g/e q. のエポキシ化合物 （2) を得た。 次 に、 フラスコ内の温度を 70°C以下まで冷却し、 ェピクロルヒ ドリン 183 9部、 ジメチルスルホキシド 1 690部を加え、 攪拌下 70°Cまで昇温し保 持した。 その後、 9 6 %水酸化ナト リウム 1 59部を 90分間かけて分割添 加した。 添加後、 さらに 3時間反応させた。 反応終了後、 過剰のェピクロル ヒ ドリン及びジメチルスルホキシドの大半を 120 °C；、 50 mmH gの減圧 下にて蒸留し、 副生塩とジメチルスルホキシ ドを含む反応生成物をメチルイ ソブチルケトンに溶解させ水洗した。 その後、 油層よりメチルイソプチルケ トンを蒸留回収して、 エポキシ当量 376 g/e q. の多核エポキシ化合物 (a— 2) を得た。 得られた多核エポキシ化合物 （a— 2) は、 エポキシ当 量から計算すると、 前記一般式 （7 a) におけるアルコール性水酸基 2. 2 8個のうち約 1. 05個がエポキシ化されている。 従って、 アルコール性水 酸基のエポキシ化率は 46 %である。 なお、 本合成例で得られた多核ェポキ シ化合物 （a— 2) の赤外線吸収スペク トル （フーリエ変換赤外分光光度計 F T - I Rを用いて測定） 及び該磁気共鳴スぺク トル （溶媒 CD C 13、 基 準物質 TMS (テトラメチルシラン） ） をそれそれ図 1及び図 2に示す。 合成例 3 In a flask equipped with a gas inlet tube, a stirrer, a condenser tube and a thermometer, 232 parts of 1,5-dihydroxynaphthylene and 3,3 ', 5,5'-epoxy equivalent of 194 g / eq. 1,4,4′-Dihydroxybiphenyldiglycidyl ether (1067 parts) was charged and dissolved at 120 ° C. with stirring under a nitrogen atmosphere. Then, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the temperature was kept at 150 ° C for about 90 minutes. Then, an epoxy compound (2) having an epoxy equivalent of 544 g / e q. Was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, 1839 parts of epichlorohydrin and 1690 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and maintained. Thereafter, 159 parts of 96% sodium hydroxide were added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After completion of the reaction, most of the excess epichlorohydrin and dimethylsulfoxide were distilled at 120 ° C under reduced pressure of 50 mmHg, and the reaction product containing the by-product salt and dimethylsulfoxide was dissolved in methylisobutylketone. Washed with water. Thereafter, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain a polynuclear epoxy compound (a-2) having an epoxy equivalent of 376 g / eq. When the obtained polynuclear epoxy compound (a-2) is calculated from the epoxy equivalent, about 1.05 of the 2.28 alcoholic hydroxyl groups in the general formula (7a) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 46%. The infrared absorption spectrum of the polynuclear epoxy compound (a-2) obtained in this synthesis example (measured using a Fourier transform infrared spectrophotometer FT-IR) and the magnetic resonance spectrum (solvent CD) C 1 3 and the reference material TMS (tetramethylsilane) are shown in Figures 1 and 2, respectively. Synthesis example 3
ガス導入管、 攪拌装置、 冷却管及び温度計を備えたフラスコに 1， 5—ジ ヒ ドロキシナフタレン 274部とエポキシ当量 1 94 g/e q . の 3 , 3 ' , 5 , 5 ' —テ トラメチルー 4, 4 ジヒ ドロキシビフエ二ルジグリシジル エーテル 1025部を仕込み、 窒素雰囲気下にて、 攪拌下 1 20°Cで溶解さ せた。 その後、 ト リフエニルホスフィン 0. 65部を添加し、 フラスコ内の 温度を 1 50°Cまで昇温し、 温度を 150°Cに保持しながら、 約 90分間反 応させ、 エポキシ当量 723 g/e q. のエポキシ化合物 （3) を得た。 次 に、 フラスコ内の温度を 70°C以下まで冷却し、 ェピクロルヒ ドリン 1 77 9部、 ジ チルスルホキシド 1 690部を加え、 攪拌下 70°Cまで昇温し保 持した。 その後、 96 %水酸化ナト リウム 1 92部を 90分間かけて分割添 加した。 添加後、 さらに 3時間反応させた。 反応終了後、 過剰のェピクロル ヒ ドリン及びジメチルスルホキシ ドの大半を 1 2 0 °C、 5 0 mmH gの減圧 下にて蒸留し、 副生塩とジメチルスルホキシドを含む反応生成物をメチルイ ソブチルケトンに溶解させ水洗した。 その後、 油層よりメチルイソプチルケ トンを蒸留回収して、 エポキシ当量 45 8 gZe q. の多核エポキシ化合物 (a— 3 ) を得た。 得られた多核エポキシ化合物 （ a— 3 ) は、 エポキシ当 量から計算すると、 前記一般式 （ 7 a) におけるアルコール性水酸基の 2. 9 3個のうち約 1. 3 2個がエポキシ化されている。 従って、 アルコール性 水酸基のエポキシ化率は 4 5 %である。 In a flask equipped with a gas inlet tube, a stirrer, a condenser tube and a thermometer, 274 parts of 1,5-dihydroxynaphthalene and 3,3 ', 5,5' with an epoxy equivalent of 194 g / eq. 1025 parts of 4,4-dihydroxybiphenyldiglycidyl ether was charged and dissolved at 120 ° C. with stirring under a nitrogen atmosphere. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C, and the epoxy equivalent was 723 g / Epoxy compound (3) of e q. was obtained. Next, the temperature in the flask was cooled to 70 ° C or less, 179 parts of epichlorohydrin and 1690 parts of ditylsulfoxide were added, and the temperature was raised to 70 ° C with stirring and maintained. Thereafter, 192 parts of 96% sodium hydroxide were dividedly added over 90 minutes. After the addition, the reaction was further performed for 3 hours. After completion of the reaction, excess epichlor Most of hydrin and dimethyl sulfoxide were distilled at 120 ° C. under reduced pressure of 50 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methylisobutyl ketone was recovered by distillation from the oil layer to obtain a polynuclear epoxy compound (a-3) having an epoxy equivalent of 458 gZeq. When the obtained polynuclear epoxy compound (a-3) was calculated from the epoxy equivalent, about 1.32 of the 2.93 alcoholic hydroxyl groups in the general formula (7a) were epoxidized. I have. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 45%.
合成例 4  Synthesis example 4
ガス導入管、 攪拌装置、 冷却管及び温度計を備えたフラスコに 2 , 6—ジ ヒ ドロキシナフ夕レン 1 6 9部とエポキシ当量 1 94 g/e q. の 3 , 3 5 , 5 ' —テ トラメチルー 4 , 4 '—ジヒ ドロキシビフェニルジグリシジル エーテル 1 1 3 0部を仕込み、 窒素雰囲気下にて、 攪拌下 1 20°Cで溶解さ せた。 その後、 ト リフエニルホスフィン 0. 6 5部を添加し、 フラスコ内の 温度を 1 5 0°Cまで昇温し、 温度を 1 5 0°Cに保持しながら、 約 9 0分間反 応させ、 エポキシ当量 3 7 1 g/e q. のエポキシ化合物 （4) を得た。 次 に、 フラスコ内の温度を 7 0°C以下まで冷却し、 ェビクロルヒ ドリン 1 9 5 2部、 ジメチルスルホキシド 1 6 9 0部を加え、 攪拌下 7 0°Cまで昇温し保 持した。 その後、 9 6 %水酸化ナトリウム 2 3 1部を 9 0分間かけて分割添 加した。 添加後、 さらに 3時間反応させた。 反応終了後、 過剰のェピクロル ヒ ドリン及びジメチルスルホキシドの大半を 1 2 0 °C、 5 0 mmH gの減圧 下にて蒸留し、 副生塩とジメチルスルホキシ ドを含む反応生成物をメチルイ ソブチルケトンに溶解させ水洗した。 その後、 油層よりメチルイソプチルケ トンを蒸留回収して、 エポキシ当量 2 6 7 g/e q . の多核エポキシ化合物 (a— 4) を得た。 得られた多核エポキシ化合物 （a— 4) は、 エポキシ当 量から計算すると、 前記一般式 （ 7 a) におけるアルコール性水酸基 1. 6 5個のうち約 0. 9 9個がエポキシ化されている。 従って、 アルコール性水 酸基のエポキシ化率は 6 0 %である。 合成例 5 ' In a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, 169 parts of 2,6-dihydroxynaphthylene and 3,35,5'-te with an epoxy equivalent of 194 g / eq. 1130 parts of tramethyl-4,4'-dihydroxybiphenyldiglycidyl ether were charged and dissolved at 120 ° C under stirring in a nitrogen atmosphere. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. An epoxy compound (4) having an epoxy equivalent of 37 1 g / e q. Was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, 195 parts of ebichlorohydrin and 169 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and maintained. Thereafter, 231 parts of 96% sodium hydroxide were added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After the completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were distilled at 120 ° C and a reduced pressure of 50 mmHg, and the reaction product containing the by-product salt and dimethyl sulfoxide was converted into methyl isobutyl ketone. Dissolved and washed with water. Thereafter, methylisobutyl ketone was distilled and recovered from the oil layer to obtain a polynuclear epoxy compound (a-4) having an epoxy equivalent of 2667 g / eq. When the obtained polynuclear epoxy compound (a-4) was calculated from the epoxy equivalent, about 0.99 of the 1.65 alcoholic hydroxyl groups in the general formula (7a) were epoxidized. . Therefore, the epoxidation rate of the alcoholic hydroxyl group is 60%. Synthesis example 5 '
9 6 %水酸化ナトリゥムの使用量を 5 8部にした以外は合成例 4と同様に して、 エポキシ当量 3 0 9 g/e q . の多核エポキシ化合物 （ a— 5 ) を得 た。 得られた多核エポキシ化合物 （ a— 5 ) は、 エポキシ当量から計算する と、 前記一般式 （ 7 a) におけるアルコール性水酸基 1. 6 5個のうち約 0. 5 0個がエポキシ化されている。 従って、 アルコール性水酸基のエポキシ化 率は 3 0 %である。  A polynuclear epoxy compound (a-5) having an epoxy equivalent of 309 g / eq. Was obtained in the same manner as in Synthesis Example 4 except that the amount of 96% sodium hydroxide used was changed to 58 parts. When the obtained polynuclear epoxy compound (a-5) is calculated from the epoxy equivalent, about 0.50 of the 1.65 alcoholic hydroxyl groups in the general formula (7a) are epoxidized. . Therefore, the epoxidation rate of the alcoholic hydroxyl group is 30%.
合成例 6  Synthesis Example 6
ガス導入管、 撹拌装置、 冷却管及び温度計を備えた反応容器に水酸基当量 8 0 g/e q . の 1 , 5—ジヒ ドロキシナフタレン 2 24. 2部とジャパン エポキシレジン （株） 製エポキシ当量 1 8 9 g/e q. のビスフエノール A 型エポキシ化合物 （商品名 「ェピコート 8 2 8」 ） 1 0 7 5. 8部を仕込み、 窒素雰囲気下にて、 撹拌下 1 1 0°Cで溶解させた。 その後、 トリフヱニルホ スフイン 0. 6 5部を添加し、 反応容器内の温度を 1 5 0°Cまで昇温し、 温 度を 1 5 0°Cで保持しながら、 約 9 0分間反応させ、 エポキシ当量 4 5 2 g /e q . のエポキシ化合物 （ 6 ) を得た。  In a reaction vessel equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, 24.2 parts of 1,5-dihydroxynaphthalene with a hydroxyl equivalent of 80 g / eq. And an epoxy equivalent of Japan Epoxy Resin Co., Ltd. 1 89 g / e q. Bisphenol A type epoxy compound (trade name “Epicoat 8 2 8”) 1 0 75.8 Charge 8 parts and dissolve at 110 ° C with stirring in a nitrogen atmosphere I let it. Then, 0.65 parts of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. An epoxy compound (6) having an equivalent weight of 452 g / eq. Was obtained.
次に、 反応容器内の温度を 40 °Cまで冷却し、 ェピクロルヒドリン 1 9 2 0部、 トルエン 1 6 9 0部を加えて溶解させた後、 テトラメチルアンモニゥ ムブロマイ ド 7 0部を添加し、 撹拌下 6 0°Cまで昇温し保持した。 その後、 48 %水酸化ナトリゥム水溶液 3 64部を 6 0分間かけて連続滴下した。 滴 下後、 さらに' 6時間反応させた。 反応終了後、 過剰の未反応ェピクロルヒド リン及びトルエンの大半を減圧蒸留により回収し、 副生塩とトルエンを含む 反応生成物をメチルイソプチルケトンに溶解させ、 水洗した。 有機溶媒層と 水層を分離した後、 有機溶媒層よりメチルイソブチルケトンを減圧蒸留して 留去し、 エポキシ当量 2 77 g/e q. の多核エポキシ化合物 （ a— 6 ) を 得た。 得られた多核エポキシ化合物 （a— 6 ) は、 エポキシ当量から計算す ると、 エポキシ化合物 （ 6 ) におけるアルコール性水酸基 1. 9 8個のうち 約 1. 5 9個がエポキシ化されている。 従って、 アルコール性水酸基のェポ キシ化率は約 80 %である。 Next, the temperature in the reaction vessel was cooled to 40 ° C., and 190 parts of epichlorohydrin and 169 parts of toluene were added and dissolved, and then 70 parts of tetramethylammonium bromide was added. Was added, and the temperature was raised to 60 ° C. with stirring and maintained. Thereafter, 364 parts of a 48% aqueous sodium hydroxide solution were continuously dropped over 60 minutes. After the addition, the reaction was continued for another 6 hours. After completion of the reaction, most of the excess unreacted epichlorohydrin and toluene were recovered by distillation under reduced pressure, and the reaction product containing the by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methyl isobutyl ketone was distilled off under reduced pressure from the organic solvent layer to obtain a polynuclear epoxy compound (a-6) having an epoxy equivalent of 277 g / eq. In the obtained polynuclear epoxy compound (a-6), when calculated from the epoxy equivalent, about 1.59 of the 1.98 alcoholic hydroxyl groups in the epoxy compound (6) were epoxidized. Therefore, alcoholic hydroxyl groups The xylation rate is about 80%.
合成例 7  Synthesis Example 7
ガス導入管、 撹拌装置、 冷却管及び温度計を備えた反応容器に水酸基当量 80 g/θ q . の 1 , 5—ジヒ ドロキシナフ夕レン 2 1 9. 2部とジャパン エポキシレジン （株） 製エポキシ当量 192 g/e q. のビキシレノール型 エポキシ化合物 （商品名 「ェピコート YX4000」 ） 1 080. 8部を仕 込み、 窒素雰囲気下にて、 撹拌下 1 10°Cで溶解させた。 その後、 ト リフエ ニルホスフィン 0. 65部を添加し、 反応容器内の温度を 1 50°Cまで昇温 し、 温度を 150°Cで保持しながら、 約 90分間反応させ、 エポキシ当量 4 5 1 g/e q . のエポキシ化合物 （ 7 ) を得た。  In a reaction vessel equipped with a gas inlet pipe, a stirrer, a cooling pipe and a thermometer, 2 19.2 parts of 1,5-dihydroxynaphthylene having a hydroxyl equivalent of 80 g / θ q. And epoxy manufactured by Japan Epoxy Resin Co., Ltd. 108.08 parts of a bixylenol-type epoxy compound having an equivalent weight of 192 g / eq. (Trade name “Epicoat YX4000”) was charged and dissolved at 110 ° C. with stirring under a nitrogen atmosphere. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. g / eq. of epoxy compound (7) was obtained.
次に、 反応容器内の温度を 40°Cまで冷却し、 ェピクロルヒ ドリン 1 89 9部、 トルエン 1 690部を加えて溶解させた後、 テ トラメチルアンモニゥ ムブロマイ ド 69部を添加し、 撹拌下 60°Cまで昇温し保持した。 その後、 48 %水酸化ナト リウム水溶液 360部を 60分間かけて連続滴下した。 滴 下後、 さらに 6時間反応させた。 反応終了後、 過剰の未反応ェピクロルヒ ド リン及びトルエンの大半を減圧蒸留により回収し、 副生塩と トルエンを含む 反応生成物をメチルイソプチルケ トンに溶解させ、 水洗した。 有機溶媒層と 水層を分離した後、 有機溶媒層よりメチルイソプチルケ トンを減圧蒸留して 留去し、 エポキシ当量 278 g/e q. の多核エポキシ化合物 （ a— 7 ) を 得た。 得られた多核エポキシ化合物 （a— 7) は、 エポキシ当量から計算す ると、 エポキシ化合物 （7) におけるアルコール性水酸基 1. 95個のうち 約 1. 56個がエポキシ化されている。 従って、 アルコール性水酸基のェポ キシ化率は約 80 %である。  Next, the temperature in the reaction vessel was cooled to 40 ° C, 189 parts of epichlorohydrin and 1690 parts of toluene were added and dissolved, and 69 parts of tetramethylammonium bromide was added, followed by stirring. The temperature was raised to and maintained at 60 ° C. Thereafter, 360 parts of a 48% aqueous sodium hydroxide solution was continuously dropped over 60 minutes. After the addition, the reaction was continued for another 6 hours. After completion of the reaction, the excess unreacted epichlorohydrin and most of the toluene were recovered by distillation under reduced pressure, and the reaction product containing the by-product salt and toluene was dissolved in methylisobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methylisobutyl ketone was distilled off from the organic solvent layer by distillation under reduced pressure to obtain a polynuclear epoxy compound (a-7) having an epoxy equivalent of 278 g / eq. In the obtained polynuclear epoxy compound (a-7), when calculated from the epoxy equivalent, about 1.56 out of 1.95 alcoholic hydroxyl groups in the epoxy compound (7) were epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is about 80%.
実施例 1〜 7及び比較例 1〜 4  Examples 1 to 7 and Comparative Examples 1 to 4
実施例 1~ 7では前記合成例 1〜 7で合成した多核エポキシ化合物 （a— 1) 〜 （a— 7) をそれそれ用い、 また比較例 1〜4では前記合成例 1〜4 で得られたエポキシ化合物 （ 1)'〜 (4) をそれぞれ用い、 表 1に示す割合 でフエノ一ル樹脂 （フエノ一ルノボラック、 水酸基当量 106 g Z e q . ) s 硬化促進剤 （ 2 —フエ二ルー 4， 5—ジヒ ドロ ミダゾ一ル、 P D M I と略記する） 及び溶剤 （カルビトールァセテ ト） を配合し、 3本口 ールミルで混練して熱硬化性樹脂組成物を'得た。 In Examples 1 to 7, the polynuclear epoxy compounds (a-1) to (a-7) synthesized in Synthesis Examples 1 to 7 were used, and Comparative Examples 1 to 4 were obtained in Synthesis Examples 1 to 4. Phenolic resin (phenol novolak, hydroxyl equivalent 106 g Z eq.) S A thermosetting resin composition is prepared by blending a curing accelerator (abbreviated as 2-phenyl-4,5-dihydromidazole, abbreviated as PDMI) and a solvent (carbitol acetate) and kneading with a 3-hole mill. I got things.
表 1 table 1
Figure imgf000044_0001
上記各実施例及び比較例の組成物を 8 0 °Cで 3 0分、 さらに 1 8 0 °Cで 1 時間の条件にて硬化させ、 ガラス転移点、 引張強度、 伸び率、 引張弾性率、 吸水率、 電気絶縁性、 鉛筆硬度を測定し、 また密着性、 耐酸性、 耐アルカリ 性を評価した。
Figure imgf000044_0001
The compositions of the above Examples and Comparative Examples were cured at 80 ° C. for 30 minutes and further at 180 ° C. for 1 hour, and the glass transition point, tensile strength, elongation, tensile modulus, Water absorption, electrical insulation, and pencil hardness were measured, and adhesion, acid resistance, and alkali resistance were evaluated.
各物性の評価は次の方法で行なった。  Each physical property was evaluated by the following methods.
くガラス転移点 > ：  Glass transition point>:
予め水洗 ·乾燥を行なったテフ口ン板に上記各実施例及び比較例の組成物 を、 スクリーン印刷法で塗布し、 熱風循環式乾燥炉で 8 0 °Cで 4 0分乾燥さ せた。 これを室温まで冷却した後、 露光量 5 0 0 m J / c m 2の条件で露光 し、 熱風循環式乾燥炉で硬化を 1 8 0 °Cで 6 0分間行なった。 これを室温ま で冷却した後、 テフロン板から硬化塗膜をはがし、 評価サンプルを得た。 こ の評価サンプルのガラス転移点を D M A法により測定した。 The compositions of the above Examples and Comparative Examples were applied by screen printing to a Tef board which had been washed and dried in advance, and dried at 80 ° C. for 40 minutes in a hot air circulation type drying oven. After cooling this to room temperature, it was exposed under the condition of an exposure amount of 500 mJ / cm 2 , and was cured in a hot air circulation type drying oven at 180 ° C. for 60 minutes. After cooling to room temperature, the cured coating film was peeled off from the Teflon plate to obtain an evaluation sample. The glass transition point of this evaluation sample was measured by the DMA method.
<引張強度 （引張破壊強さ） 、 伸び率 （引張破壊伸び） 、 引張弾性率 > ： J I S K 7 1 2 7に準拠して求めた。 <Tensile strength (tensile breaking strength), elongation (tensile breaking elongation), tensile modulus>: It was determined in accordance with JISK 7127.
<吸水率、 鉛筆硬度 > ：  <Water absorption, pencil hardness>:
J I S K 5 4 0 0に準拠して求めた。  It was determined in accordance with JIS K540.
<密着性> ：  <Adhesion>
J I S D 0 2 0 2に準拠して目視判定した。 判定基準は以下のとおり である。  It was determined visually based on JISD202. The criteria are as follows.
〇 ：全く剥がれが認められないもの  〇: No peeling is observed at all
△ ： ほんの僅か剥がれたもの  △: slightly peeled
X ：完全に剥がれたもの  X: Completely peeled
く電気絶縁性 > ：  Electrical insulation>:
上記各実施例及び比較例の組成物を、 I P C B— 2 5のクシ型電極 Bク —ボンにパイ口ッ ト精ェ （株） 製口一ルコ一夕一を用いて全面に塗布し、 80 で 3 0分、 さらに 1 8 0 °Cで 1時間硬化させ、 評価基板を作製した。 こ のクシ型電極に; D C 5 0 0 Vのバイァス電圧を印加し、 絶縁抵抗値を測定し た。  The composition of each of the above Examples and Comparative Examples was applied to the entire surface of the comb-shaped electrode B-cup of IPCB-25 using Pachi-Koto Seie Co., Ltd. The substrate was cured for 30 minutes at 180 ° C. for 1 hour to prepare an evaluation substrate. A bias voltage of DC500 V was applied to this comb-shaped electrode, and the insulation resistance was measured.
<耐酸性試験 > ：  <Acid resistance test>:
電気絶縁性に用いたのと同じ評価基板を 1 0容量％硫酸水溶液に 2 0 °Cで 3 0分間浸漬後取り出し、 塗膜の状態と 着性とを総合的に判定評価した。 判定基準は以下のとおりである。  The same evaluation substrate used for electrical insulation was immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C. for 30 minutes, taken out, and the state and adhesion of the coating film were comprehensively evaluated. The criteria are as follows.
〇 ：変化が認められないもの  〇: No change is observed
△： ほんの僅か変化しているもの  △: only slight change
X ：塗膜にフクレあるいは膨潤脱落があるもの  X: The coating film has blisters or swelling and falling off
<耐アル力リ性試験 > ：  <Al-resistance test>:
1 0容量％硫酸水溶液を 1 0容量％水酸化ナト リゥム水溶液に変えたこと 以外は耐酸性試験と同様に試験評価した。  The test and evaluation were conducted in the same manner as the acid resistance test, except that the 10% by volume aqueous sulfuric acid solution was changed to a 10% by volume aqueous sodium hydroxide solution.
得られた結果を表 2に示す。 表 2 Table 2 shows the obtained results. Table 2
実 施 例 比 較 例  Example Example Comparative Example
は  Is
1 2 3 4 5 6 7 1 2 3 4 ガラス転移点  1 2 3 4 5 6 7 1 2 3 4 Glass transition point
( 。c) 189.4 180.1 173.5 198.8 190.5 204.5 213.1 168.1 166.3 165.1 172.4 (.C) 189.4 180.1 173.5 198.8 190.5 204.5 213.1 168.1 166.3 165.1 172.4
Hfι HE H ιψ¾ ¾ 1土千 ^ Hfι HE H ιψ¾ ¾ 1 Dozen ^
丄 y t ο . 丄 y Q 9 . Δ 丄 Q 8 Q y O .4 Λ  T y t ο. 丄 y Q 9. Δ 丄 Q 8 Q y O .4
丄 y t»丄 .8 丄 y Ob .c5 Q O Π Q O f A C  丄 y t »丄 .8 丄 y Ob .c5 Q O Π Q O f A C
iy (j / . o 丄 4^ . u iy (j / .o 丄 4 ^ .u
(N/mm2 ) (N / mm 2 )
引張強度 Tensile strength
62.9 62.3 61.6 63.2 62.8 69.4 70.2 62.1 61.6 60.8 62.5 (N/mm2 ) 62.9 62.3 61.6 63.2 62.8 69.4 70.2 62.1 61.6 60.8 62.5 (N / mm 2 )
伸び率 （％) 5.61 5.64 5.71 5.58 5.62 5.11 5.32 5.64 5.66 5.69 5.61 吸水率 （％) 0.61 0.66 0.73 0.58 0.60 0.66 0.71 1.05 1.10 1.18 1.04 密着性 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 電気絶縁抵抗 Elongation (%) 5.61 5.64 5.71 5.58 5.62 5.11 5.32 5.64 5.66 5.69 5.61 Water absorption (%) 0.61 0.66 0.73 0.58 0.60 0.66 0.71 1.05 1.10 1.18 1.04 Adhesion 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 Electrical insulation resistance
3.7 3.4 3.5 4.0 3.9 3.5 3.7 3.4 3.3 3.3 3.5 ( x l 0 1 3 Ω ) 3.7 3.4 3.5 4.0 3.9 3.5 3.7 3.4 3.3 3.3 3.5 (xl 0 13 Ω)
鉛筆硬度 6H 6H 5H 7H 6H 6H 6H 3H 3H 2H 3H 耐酸性 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 耐ァルカ リ性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Pencil hardness 6H 6H 5H 7H 6H 6H 6H 3H 3H 2H 3H Acid resistance 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 Alkaline resistance 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇
表 2に示す結果から明らかなように、 本発明の多核エポキシ化合物から得 られた硬化物は、 高いガラス転移点を有し、 機械的強度に優れ、 吸水率、 密 着性、 電気絶縁抵抗、 硬度、 耐薬品性等にも優れた特性を有している。 これ に対して、 比較例の芳香族エポキシ化合物から得られた硬化物は、 ガラス転 移点が低く、 吸水率、 硬度等が劣っていた。 As is clear from the results shown in Table 2, the cured product obtained from the polynuclear epoxy compound of the present invention has a high glass transition point, excellent mechanical strength, water absorption, adhesion, electrical insulation resistance, It has excellent properties such as hardness and chemical resistance. On the other hand, the cured product obtained from the aromatic epoxy compound of the comparative example had a low glass transition point and was inferior in water absorption, hardness and the like.
合成例 8  Synthesis Example 8
ガス導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコに 1 , 5—ジ ヒ ドロキシナフ夕レン 1 6 9部とエポキシ当量 1 94 g/e q . の 3， 3 ' , 5， 5 ' —テトラメチルー 4 , 4 ' ージヒ ドロキシビフエ二ルジグリシジル エーテル 1 1 3 0部を仕込み、 窒素雰囲気下にて、 撹袢下 1 2 0°Cで溶解さ せた。 その後、 ト リフエニルホスフィン 0. 6 5部を添加し、 フラスコ内の 温度を 1 5 0でまで昇温し、 温度を 1 5 0°Cで保持しながら、 約 9 0分間反 応させ、 エポキシ当量 3 5 0 g/e q. のエポキシ化合物 （ 8 ) を得た。 次 にフラスコ内の温度を 7 0 °C以下まで冷却し、 ェピクロルヒ ドリ ン 2 0 8 0 部、 ジメチルスルホキシド 1 6 9 0部を加え、 撹拌下 70°Cまで昇温し保持 した。 その後、 9 6 %水酸化ナト リウム 1 8 0部を 9 0分間かけて分割添加 した。 添加後、 さらに 3時間反応させた。 反応終了後、 過剰のェピクロルヒ ドリン及ぴジメチルスルホキシドの大半を 1 2 0 °C、 5 0 mmH gの減圧下 にて蒸留し、 副生塩とジメチルスルホキシドを含む反応生成物をメチルイソ プチルケトンに溶解させ水洗した。 その後、 油層よりメチルイソプチルケ ト ンを蒸留回収して、エポキシ当量 2 6 2 g//e q.の多核エポキシ化合物（a — 8) を得た。 得られた多核エポキシ化合物 （a— 8 ) は、 エポキシ当量か ら計算すると、 一般式 （ 7 a) におけるアルコール性水酸基 1. 5 7個のう ち約 0. 8 6個がエポキシ化されている。 従って、 アルコール性水酸基のェ ポキシ化率は 5 5 %である。  In a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, 169 parts of 1,5-dihydroxynaphthylene and 3, 3 ', 5, 5' with an epoxy equivalent of 194 g / eq. Thirty-one parts of tetramethyl-4,4'dihydroxybiphenyldiglycidyl ether were charged and dissolved at 120 ° C. under a nitrogen atmosphere with stirring. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. An epoxy compound (8) having an equivalent weight of 350 g / e q. Was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, 280 parts of epichlorohydrin and 169 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and maintained. Thereafter, 180 parts of 96% sodium hydroxide was added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were distilled at 120 ° C under reduced pressure of 50 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone. Washed with water. Thereafter, methylisobutyl ketone was recovered by distillation from the oil layer to obtain a polynuclear epoxy compound (a-8) having an epoxy equivalent of 262 g // eq. When the obtained polynuclear epoxy compound (a-8) was calculated from the epoxy equivalent, about 0.86 out of 1.57 alcoholic hydroxyl groups in the general formula (7a) were epoxidized. . Therefore, the epoxidation rate of alcoholic hydroxyl groups is 55%.
次に、 多核エポキシ化合物 （a— 8) 47 1部を、 撹拌装置、 冷却管及び 温度計を備えたフラスコに入れ、 カルビトールアセテート 400部を加え、 加熱溶解し、 メチルハイ ドロキノン 0. 4 6部と、 ト リフエニルホスフィ ン 1 . 3 8部を加え、 9 5〜 1 0 5 °Cに加熱し、 アクリル酸 1 2 9部を徐々に 滴下し、 1 6時間反応させた。 以下、 この反応溶液を b— 1ワニスと称す。 なお、 本合成例で得られた多核エポキシァクリレート化合物 （b— 1 ) の赤 外線吸収スぺク トル（フ一リェ変換赤外分光光度計 F T— I Rを用いて測定） 及び核磁気共鳴スぺク トル （溶媒 C D C 1 3 s 基準物質 T M S (テ トラメチ ルシラン） ） をそれそれ図 3及び図 4に示す。 Next, 47 parts of the polynuclear epoxy compound (a-8) was placed in a flask equipped with a stirrer, a condenser and a thermometer, and 400 parts of carbitol acetate was added. The mixture was heated and dissolved, and 0.46 parts of methylhydroquinone was added. And trifenylphosphine 1.38 parts were added, and the mixture was heated to 95 to 105 ° C., and 129 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. Hereinafter, this reaction solution is referred to as b-1 varnish. The infrared absorption spectrum of the polynuclear epoxy acrylate compound (b-1) obtained in this synthesis example (measured using a Fourier transform infrared spectrophotometer FT-IR) and nuclear magnetic resonance The spectra (solvent CDC 13 s reference material TMS (tetramethylsilane)) are shown in Figures 3 and 4, respectively.
合成例 9  Synthesis Example 9
合成例 8で得られた多核エポキシ化合物（a— 8 ) 5 2 8部を、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールアセテート 4 0 0 部を加え、 加熱溶解し、 メチルハイ ドロキノン 0 . 4 6部と、 トリフエニル ホスフィン 1 . 3 8部を加え、 9 5〜 1 0 5 °Cに加熱し、 アクリル酸 7 2部 を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b— 2ワニス と称す。  528 parts of the polynuclear epoxy compound (a-8) obtained in Synthesis Example 8 was placed in a flask equipped with a stirrer, a condenser, and a thermometer, and 400 parts of carbitol acetate was added, followed by heating and dissolving. 0.46 parts of methylhydroquinone and 1.38 parts of triphenyl phosphine were added, and the mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. Hereinafter, this reaction solution is referred to as b-2 varnish.
合成例 1 0  Synthesis example 10
合成例 3で得られた多核エポキシ化合物（a — 3 ) 5 1 8部を、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールアセテート 4 0 0 部を加え、 加熱溶解し、 メチルハイ ドロキノン 0 . 4 6部と、 ト リフエニル ホスフィン 1 . 3 8部を加え、 9 5〜 1 0 5 °Cに加熱し、 アクリル酸 8 2部 を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b— 3ワニス と称す。  518 parts of the polynuclear epoxy compound (a-3) obtained in Synthesis Example 3 was placed in a flask equipped with a stirrer, a condenser, and a thermometer, and 400 parts of carbitol acetate was added. 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added, and the mixture was heated to 95 to 105 ° C., and 82 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. Hereinafter, this reaction solution is referred to as b-3 varnish.
合成例 1 1  Synthesis example 1 1
合成例 4で得られた多核エポキシ化合物 （a— 4 ) 4 7 3部を、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールァセテ一ト 4 0 0 部を加え、 加熱溶解し、 メチルハイ ドロキノン 0 . 4 6部と、 ト リフヱニル ホスフィン 1 . 3 8部を加え、 9 5〜 1 0 5 °Cに加熱し、 ァクリル酸 1 2 7 部を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b— 4ヮニ スと称す。  473 parts of the polynuclear epoxy compound (a-4) obtained in Synthesis Example 4 was placed in a flask equipped with a stirrer, a condenser, and a thermometer, and 400 parts of carbitol acetate was added, followed by heating. Dissolve, add 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine, heat to 95-105 ° C, gradually add 127 parts of acrylic acid, and add for 16 hours Reacted. Hereinafter, this reaction solution is referred to as b-4 ヮ.
合成例 1 2 合成例 6で得られた多核エポキシ化合物 （ a— 6 ) 2 7 7部を撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールァセテ一ト 2 3 3 部を加え、 加熱溶解し、 メチルハイ ドロキノン 0. 46部と、 ト リフエニル ホスフィン 1. 3 8部を加え、 9 5〜 1 0 5 °Cに加熱し、 アクリル酸 7 2部 を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b— 5ワニス と称す。 Synthesis example 1 2 277 parts of the polynuclear epoxy compound (a-6) obtained in Synthesis Example 6 was placed in a flask equipped with a stirrer, a condenser and a thermometer, and 233 parts of carbitol acetate was added, followed by heating and dissolution. Then, 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine were added, and the mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. . Hereinafter, this reaction solution is referred to as b-5 varnish.
合成例 1 3  Synthesis Example 1 3
合成例 7で得られた多核エポキシ化合物 （ a— 7 ) 2 7 8部を撹袢装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールァセテ一ト 2 3 3 部を加え、 加熱溶解し、 メチルハイ ドロキノン 0. 46部と、 ト リフエニル ホスフィン 1. 3 8部を加え、 9 5〜 1 0 5 °Cに加熱し、 アクリル酸 7 2部 を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b— 6ワニス と称す。  278 parts of the polynuclear epoxy compound (a-7) obtained in Synthesis Example 7 was placed in a flask equipped with a stirrer, a cooling tube and a thermometer, and 233 parts of carbitol acetate was added, followed by heating. Dissolve, add 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine, heat to 95 to 105 ° C, gradually add 72 parts of acrylic acid dropwise, and react for 16 hours. Was. Hereinafter, this reaction solution is referred to as b-6 varnish.
比較合成例 1  Comparative Synthesis Example 1
クレゾ一ルノボラヅク型エポキシ樹脂 （ェピクロン N— 6 9 5、 大日本ィ ンキ化学工業 （株） 製、 エポキシ当量 2 2 0 g/e q. ) 5 27部を、 ガス 導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトー ルァセテート 3 0 0部を加え、 加熱溶解し、 ハイ ドロキノン 0. 4 6部と、 ト リフエニルホスフィン 1. 3 8部を加えた。 この混合物を 9 5〜 1 0 5。C に加熱し、 アクリル酸 1 7 3部を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b' — 1ワニスと称す。  Cresol novolak type epoxy resin (Epiclone N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 220 g / eq.) 5 27 parts of gas introduction pipe, stirrer, cooling pipe Then, the mixture was placed in a flask equipped with a thermometer, 300 parts of carbitol acetate was added, and the mixture was heated and dissolved, and 0.446 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. 95-105 of this mixture. C., and 173 parts of acrylic acid were gradually added dropwise, and the mixture was reacted for 16 hours. Hereinafter, this reaction solution is referred to as b′-1 varnish.
比較合成例 2  Comparative Synthesis Example 2
クレゾ一ルノボラヅク型エポキシ樹脂 （ェビクロン N— 6 9 5、 大日本ィ ンキ化学工業 （株） 製、 エポキシ当量 2 2 0 g/e q . ) 6 02部を、 ガス 導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビト一 ルアセテート 3 0 0部を加え、 加熱溶解し、 ハイ ドロキノン 0. 4 6部と、 トリフエニルホスフィ ン 1. 3 8部を加えた。 この混合物を 9 5〜 1 0 5 °C に加熱し、 アクリル酸 9 8部を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b ' — 2ワニスと称す。 Cresol novolak type epoxy resin (Evicron N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 220 g / eq.) 600 parts of a gas introduction pipe, a stirrer, a cooling pipe and In a flask equipped with a thermometer, 300 parts of carbitol acetate was added, and the mixture was heated and dissolved, and 0.446 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C., and 98 parts of acrylic acid was gradually added dropwise to react for 16 hours. Less than, This reaction solution is referred to as b'-2 varnish.
比較合成例 3  Comparative Synthesis Example 3
フエノールノボラック型エポキシ樹脂 （E P P N— 2 0 1、 日本化薬（株） 製、 エポキシ当量 1 9 0 g/e q . ) 5 0 8部を、 ガス導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールアセテート 3 0 0 部を加え、 加熱溶解し、 ハイ ドロキノン 0. 4 6部と、 ト リフエニルホスフ イ ン 1. 3 8部を加えた。 この混合物を 9 5 ~ 1 0 5でに加熱し、 アクリル 酸.1 9 2部を徐々に滴下し、 1 6時間反応させた。 以下、 この反応溶液を b 5 一 3ワニスと称す。 A phenol novolak type epoxy resin (EPPN-201, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 190 g / eq.) 508 parts is equipped with a gas introduction pipe, a stirrer, a cooling pipe and a thermometer. Then, 300 parts of carbitol acetate was added, and the mixture was heated and dissolved, and 0.446 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105, and .192 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. Hereinafter referred to the reaction solution and the b 5 one 3 varnish.
比較合成例 4  Comparative Synthesis Example 4
ガス導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコにビスフエノ —ル A 3 1 3部とビスフエノ一ル A型エポキシ樹脂 （ェビクロン一 8 4 0、 大日本ィンキ化学工業 （株） 製、 エポキシ当量 1 8 0 g/e q . ) 9 8 7部 を仕込み、 窒素雰囲気下にて、 撹袢下 1 2 0°Cで溶解させた。 その後、 ト リ フエニルホスフィ ン 0. 6 5部を添加し、 フラスコ内の温度を 1 5 0°Cまで 昇温し、 温度を 1 5 0°Cで保持しながら、 約 9 0分間反応させ、 エポキシ当 量 4 7 5 g/e q . のエポキシ化合物 （ g) を得た。 次にフラスコ内の温度 を 7 0°C以下まで冷却し、 ェピクロルヒ ドリン 1 8 5 1部、 ジメチルスルホ キシド 1 6 9 0部を加え、撹拌下 7 0°Cまで昇温し保持した。その後、 9 6 % 水酸化ナト リウム 1 1 0部を 9 0分間かけて分割添加した。 添加後、 さらに 3時間反応させた。 反応終了後、 過剰のェピクロルヒ ドリ ン及びジメチルス ルホキシドの大半を 1 2 0°C、 5 0 mmH gの減圧下にて蒸留し、 副生塩と ジメチルスルホキシドを含む反応生成物をメチルイソブチルケトンに溶解さ せ水洗した。 その後、 油層よりメチルイソプチルケトンを蒸留回収して、 ェ ポキシ当量 3 3 6 g/e q . のエポキシ化合物 （h) を得た。 得られたェポ キシ化合物 （h) は、 エポキシ当量から計算すると、 一般式 （ 6 ) (但し、 X = Y) におけるアルコール性水酸基 2. 0 0個のうち約 0. 9個がェポキ シ化されている。 従って、 アルコール性水酸基のエポキシ化率は 4 5 %であ る o In a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, add bisphenol A313 and bisphenol A type epoxy resin (Evicron 840, manufactured by Dainippon Ink & Chemicals, Inc.) Epoxy equivalent (180 g / eq.) 987 parts was charged and dissolved at 120 ° C under a nitrogen atmosphere with stirring. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. An epoxy compound (g) having an equivalent of 475 g / eq. Was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, 185 parts of epichlorohydrin and 169 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and maintained. Thereafter, 110 parts of 96% sodium hydroxide was added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After the completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were distilled at 120 ° C under reduced pressure of 50 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone. It was washed with water. Thereafter, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy compound (h) having an epoxy equivalent of 336 g / eq. When the obtained epoxy compound (h) was calculated from the epoxy equivalent, about 0.9 of the 2.0 alcoholic hydroxyl groups in the general formula (6) (where X = Y) were epoxidized. Have been. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 45%. O
次に、 エポキシ化合物 （h) 4 9 4部を撹拌装置、 冷却管及び温度計を備 えたフラスコに入れ、 カルビトールアセテート 40 0部を加え、加熱溶解し、 メチルハイ ドロキノン 0. 4 6部と、 トリフエニルホスフィ ン 1. 3 8部を 加え、 9 5〜 1 0 5 °Cに加熱し、 アクリル酸 1 0 6部を徐々に滴下し、 1 6 時間反応させた。 以下、 この反応溶液を b' — 4ワニスと称す。  Next, 494 parts of the epoxy compound (h) was placed in a flask equipped with a stirrer, a condenser, and a thermometer, and 400 parts of carbitol acetate was added. The mixture was heated and dissolved, and 0.46 parts of methylhydroquinone was added. To the mixture was added 1.38 parts of triphenylphosphine, and the mixture was heated to 95 to 105 ° C., and 106 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. Hereinafter, this reaction solution is referred to as b'-4 varnish.
実施例 8〜 1 3及び比較例 5〜 8  Examples 8 to 13 and Comparative Examples 5 to 8
前記合成例 8〜 1 3及び比較合成例 1〜4で得られた各ワニスを用いた表 3に示す配合成分を、 3本ロールミルで混練し、 光硬化性及び熱硬化性樹脂 組成物を得た。  The components shown in Table 3 using the varnishes obtained in Synthesis Examples 8 to 13 and Comparative Synthesis Examples 1 to 4 were kneaded with a three-roll mill to obtain a photocurable and thermosetting resin composition. Was.
表 3  Table 3
Figure imgf000051_0001
Figure imgf000051_0001
ィル ュア一 9 07 ： 2—メチルー 1一 [4—(メチルチオ）フェニル] 一  9-07: 2-Methyl-1-1 [4- (methylthio) phenyl]-
2—モルホリノアミノプロパノン一 1  2-morpholinoaminopropanone 1
(チバ · スペシャルティ · ケミカルズ社製光重合開始剤） I T X ： イソプロピルチオキサントン （日本化薬 （株） 製）  (Photopolymerization initiator manufactured by Ciba Specialty Chemicals) I T X: Isopropylthioxanthone (Nippon Kayaku Co., Ltd.)
DPHA ： ジペンタエリスリ トールへキサァクリレート （日本化薬 （株） 製） S - 6 6 ： シリコ—ン系消泡剤 （信越化学工業 （株） 製）  DPHA: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) S-66: Silicone antifoam (Shin-Etsu Chemical Co., Ltd.)
R— 9 7 4 ：微粉シリカ （日本ァエロジル （株） 製） 上記各実施例及び比較例の組成物を 8 0 °Cで 3 0分乾燥させ、 露光量 5 0 O m J / c m 2の条件で露光し、 硬化させ、 また、 さらに実施例 9及び比較 例 6については露光後、 1 5 0 °Cで 1時間硬化させ、 前記と同様の方法によ りガラス転移点、 引張弾性率、 引張強度、 伸び率、 吸水率、 鉛筆硬度、 電気 絶縁抵抗を測定し、 また、 密着性、 耐酸性、 耐アルカリ性を評価した。 評価 結果を表 4に示す。 表 4 R-974: Fine silica (Nippon Aerosil Co., Ltd.) The compositions of each of the above Examples and Comparative Examples were dried at 80 ° C. for 30 minutes, exposed at an exposure amount of 50 O m J / cm 2 , and cured, and further, Example 9 and Comparative Examples For 6, after exposure, cure at 150 ° C for 1 hour and measure glass transition point, tensile modulus, tensile strength, elongation, water absorption, pencil hardness, and electrical insulation resistance by the same method as above In addition, adhesion, acid resistance, and alkali resistance were evaluated. Table 4 shows the evaluation results. Table 4
Figure imgf000052_0001
表 4に示す結果から明らかな如く、 本発明の多核エポキシァクリレート化 合物から得られた硬化物は、 高いガラス転移点を有し、 機械的強度に優れ、 吸水率、 密着性、 電気絶縁抵抗、 硬度、 耐薬品性等にも優れた特性を有して いる。 これに対して、 比較例の芳香族エポキシァクリレート化合物から得ら れた硬化物は、 ガラス転移点、 吸水率、 硬度等が劣っていた。
Figure imgf000052_0001
As is clear from the results shown in Table 4, the cured product obtained from the polynuclear epoxy acrylate compound of the present invention has a high glass transition point, excellent mechanical strength, water absorption, adhesion, and electric It has excellent properties such as insulation resistance, hardness and chemical resistance. On the other hand, the cured product obtained from the aromatic epoxy acrylate compound of Comparative Example was inferior in glass transition point, water absorption, hardness and the like.
合成例 1 4  Synthesis Example 1 4
合成例 8で得られた多核エポキシ化合物 （a— 8 ) 3 1部を、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールァセテ一ト 4 0 0 部を加え、 加熱溶解し、 メチルハイ ドロキノ ン 0 . 4 6部と、 トリフエニル ホスフィン 1. 38部を加え、 95〜 105 °Cに加熱し、 アクリル酸 94部 を徐々に滴下し、 1 6時間反応させた。 この反応生成物を、 80〜90°Cま で冷却し、テ トラヒ ドロフ夕ル酸無水物 1 66部を加え、 8時間反応させた。 反応は、 電位差滴定による反応液の酸化、 全酸化測定を行ない、 得られる付 加率にて追跡し、 反応率 95 %以上を終点とする。 このようにして得られた カルボキシル基含有活性エネルギー線硬化性樹脂は、 固形物の酸価 102m gK〇H/gであった。 以下、 この反応溶液を A— 1ワニスと称す。 なお、 本合成例で得られた力ルボキシル基含有活性ェネルギ一線硬化性樹脂 （ A— 1) の赤外線吸収スぺク トル （フーリエ変換赤外分光光度計 FT— I Rを用 いて測定）及び核磁気共鳴スぺク トル {溶媒 CD C 13、 基準物質 TMS (テ トラメチルシラン） } をそれそれ図 5及び図 6に示す。 31 parts of the polynuclear epoxy compound (a-8) obtained in Synthesis Example 8 was placed in a flask equipped with a stirrer, a condenser, and a thermometer, and 400 parts of carbitol acetate was added, followed by heating and dissolution. 0.46 parts of methylhydroquinone and trifenyl 1.38 parts of phosphine was added, and the mixture was heated to 95 to 105 ° C., and 94 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 166 parts of tetrahydrofuroic anhydride was added, and the mixture was reacted for 8 hours. In the reaction, the reaction solution is oxidized by potentiometric titration and total oxidation is measured, and the reaction is followed by the obtained addition rate. The carboxyl group-containing active energy ray-curable resin thus obtained had an acid value of solid of 102 mgK〇H / g. Hereinafter, this reaction solution is referred to as A-1 varnish. The infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) and the nuclear magnetic field of the active energy linear curing resin (A-1) obtained in the present synthesis example were obtained. resonance scan Bae-vector {solvents CD C 1 3, reference material TMS (Te tetramethyl silane)} shows a thereto it FIGS. 5 and 6.
合成例 15  Synthesis Example 15
ガス導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコに 1 , 5—ジ ヒ ドロキシナフ夕レン 203部とビスフエノール A型エポキシ樹脂 （ェピク ロン— 840、 大日本ィンキ化学工業 （株） 製、 エポキシ当量 180 g/e q. ) 109 7部を仕込み、 窒素雰囲気下にて、 撹拌下 120°Cで溶解させ た。 その後、 ト リフエニルホスフィ ン 0. 65部を添加し、 フラスコ内の温 度を 1 50°Cまで昇温し、 温度を 1 50°Cで保持しながら、 約 90分間反応 させ、 エポキシ当量 36 5 g/e q . のエポキシ化合物 （ 15) を得た。 次 に、 フラスコ内の温度を 70°C以下まで冷却し、 ェピクロルヒ ドリン 205 8部、 ジメチルスルホキシド 1 690部を加え、 撹拌下 70°Cまで昇温し保 持した。 その後、 96 %水酸化ナト リウム 122部を 90分間かけて分割添 加した。 添加後、 さらに 3時間反応させた。 反応終了後、 過剰のェビクロル ヒ ドリン及びジメチルスルホキシ ドの大半を 1 20 °C、 50 mmH gの減圧 下にて蒸留し、 副生塩とジメチルスルホキシドを含む反応生成物をメチルイ ソプチルケトンに溶解させ水洗した。 その後、 油層よりメチルイソプチルケ トンを蒸留回収して、 エポキシ当量 275 g/e q. の多核エポキシ化合物 (a- 1 5) を得た。 得られた多核エポキシ化合物 （a— 1 5) は、 ェポキ シ当量から計算すると、 前記一般式 （ 7 b) におけるアルコ—ル性水酸基 1. 7 1個のうち約 0. 8 2個がエポキシ化されている。 従って、 アルコール性 水酸基のエポキシ化率は 48 %である。 In a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, 203 parts of 1,5-dihydroxynaphthylene and bisphenol A-type epoxy resin (Epiclon-840, manufactured by Dainippon Ink & Chemicals, Inc.) , Epoxy equivalent 180 g / e q.) 109 7 parts were charged and dissolved at 120 ° C. under stirring in a nitrogen atmosphere. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. 365 g / eq. Of epoxy compound (15) was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, and epichlorohydrin 205 (8 parts) and dimethyl sulfoxide (1690 parts) were added. The mixture was heated to 70 ° C. under stirring and maintained. Thereafter, 122 parts of 96% sodium hydroxide was dividedly added over 90 minutes. After the addition, the reaction was further performed for 3 hours. After the completion of the reaction, most of the excess ebichlorohydrin and dimethylsulfoxide are distilled at 120 ° C under a reduced pressure of 50 mmHg, and the reaction product containing the by-product salt and dimethylsulfoxide is dissolved in methylisobutylketone. Washed with water. Thereafter, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain a polynuclear epoxy compound (a-15) having an epoxy equivalent of 275 g / eq. The resulting polynuclear epoxy compound (a-15) was When calculated from the siquivalent weight, about 0.82 of the 1.71 alcoholic hydroxyl groups in the general formula (7b) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 48%.
次に、 多核エポキシ化合物 （a— 1 5 ) 347部を撹拌装置、 冷却管及び 温度計を備えたフラスコに入れ、 カルビトールアセテート 400部を加え、 加熱溶解し、 メチルハイ ドロキノン 0. 4 6部と、 トリフエニルホスフィ ン 1. 3 8部を加え、 9 5〜 1 0 5°Cに加熱し、 アクリル酸 9 1部を徐々に滴 下し、 1 6時間反応させた。 この反応生成物を、 8 0〜 9 0°Cまで冷却.し、 テトラヒ ドロフ夕ル酸無水物 1 6 3部を加え、 8時間反応させた。 反応は、 電位差滴定による反応液の酸化、 全酸化測定を行ない、 得られる付加率にて 追跡し、 反応率 9 5 %以上を終点とする。 このようにして得られたカルボキ シル基含有活性エネルギー線硬化性樹脂は、 固形物の酸価 1 O O mgK OH / であった。 以下、 この反応溶液を A— 2ワニスと称す。  Next, 347 parts of the polynuclear epoxy compound (a-15) was placed in a flask equipped with a stirrer, a condenser and a thermometer, and 400 parts of carbitol acetate was added. The mixture was heated and dissolved, and 0.46 parts of methylhydroquinone was added. Then, 1.38 parts of triphenylphosphine was added, and the mixture was heated to 95 to 105 ° C., and 91 parts of acrylic acid was gradually dropped to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., and thereto was added 163 parts of tetrahydrofuroic anhydride, followed by a reaction for 8 hours. In the reaction, the reaction solution is oxidized by potentiometric titration and total oxidation is measured. The reaction is followed at the obtained addition rate, and the reaction rate is determined to be 95% or more. The carboxyl group-containing active energy ray-curable resin thus obtained had a solid acid value of 1 O O mgK OH /. Hereinafter, this reaction solution is referred to as A-2 varnish.
合成例 1 6  Synthesis Example 1 6
ガス導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコにビスフヱノ —ル A 2 2 2部とエポキシ当量 1 94 g/e q. の 3， 3 ' , 5 , 5 ' —テ トラメチルー 4 , 4 ' —ジヒ ドロキシビフエ二ルジグリシジルエーテル 1 0 7 8部を仕込み、 窒素雰囲気下にて、 撹拌下 1 2 0°Cで溶解させた。 その後、 ト リフエニルホスフィ ン 0. 6 5部を添加し、 フラスコ内の温度を 1 5 0°C まで昇温し、 温度を 1 5 0°Cで保持しながら、 約 9 0分間反応させ、 ェポキ シ当量 3 6 0 g/e q . のエポキシ化合物 （ 1 6 ) を得た。 次に、 フラスコ 内の温度を 7 0 °C以下まで冷却し、 ェビクロルヒ ドリン 1 8 77部、 ジメチ ルスルホキシ ド 1 6 9 0部を加え、 撹拌下 7 0°Cまで昇温し保持した。 その 後、 9 6 %水酸化ナト リウム 1 1 1部を 9 0分間かけて分割添加した。 添加 後、 さらに 3時間反応させた。 反応終了後、 過剰のェピクロルヒ ドリン及び ジメチルスルホキシドの大半を 1 2 0°C、 5 0 mm H gの減圧下にて蒸留し、 副生塩とジメチルスルホキシドを含む反応生成物をメチルイソブチルケ トン に溶解させ水洗した。 その後、 油層よりメチルイソプチルケトンを蒸留回収 して、 エポキシ当量 2 7 6 g/e q. の多核エポキシ化合物 （a— 1 6 ) を 得た。 得られた多核エポキシ化合物 （a— 1 6 ) は、 エポキシ当量から計算 すると、 前記一般式 （ 6 ) におけるアルコール性水酸基 1. 54個のうち約 0. 77個がエポキシ化されている。 従って、 アルコール性水酸基のェポキ シ化率は 5 0 %である。 In a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, add 2 parts of bisphenol A and 3, 3 ', 5, 5' with an epoxy equivalent of 194 g / eq.-tetramethyl-4, 107 ′ parts of 4′-dihydroxybiphenyl diglycidyl ether were charged and dissolved at 120 ° C. with stirring under a nitrogen atmosphere. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. Thus, an epoxy compound (16) having an epoxy equivalent of 360 g / eq. Was obtained. Next, the temperature in the flask was cooled to 70 ° C. or lower, 1877 parts of ebichlorohydrin and 169 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and maintained. Thereafter, 111 parts of 96% sodium hydroxide was added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After completion of the reaction, most of the excess epichlorohydrin and dimethylsulfoxide were distilled at 120 ° C under reduced pressure of 50 mmHg, and the reaction product containing the by-product salt and dimethylsulfoxide was converted to methylisobutylketone. Dissolved and washed with water. After that, methyl isobutyl ketone is recovered by distillation from the oil layer. As a result, a polynuclear epoxy compound (a-16) having an epoxy equivalent of 276 g / e q. Was obtained. In the obtained polynuclear epoxy compound (a-16), when calculated from the epoxy equivalent, about 0.77 out of 1.54 alcoholic hydroxyl groups in the general formula (6) were epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 50%.
次に、 多核エポキシ化合物 （a— 1 6 ) 34 9部を、 撹拌装置、 冷却管及 び温度計を備えたフラスコに入れ、カルビトールアセテート 400部を加え、 加熱溶解し、 メチルハイ ドロキノン 0. 4 6部と、 ト リフエニルホスフィ ン 1. 3 8部を加え、 9 5〜 1 0 5°Cに加熱し、 アクリル酸 9 1部を徐々に滴 下し、 1 6時間反応させた。 この反応生成物を、 8 0〜 9 0°Cまで冷却し、 テトラヒ ドロフタル酸無水物 1 5 9部を加え、 8時間反応させた。 反応は、 電位差滴定による反応液の酸化、 全酸化測定を行ない、 得られる付加率にて 追跡し、 反応率 9 5 %以上を終点とする。 このようにして得られたカルボキ シル基含有活性エネルギー線硬化性樹脂は、 固形物の酸価 9 8mgKOH/ gであった。 以下、 この反応溶液を A— 3ワニスと称す。  Next, 349 parts of the polynuclear epoxy compound (a- 16) was placed in a flask equipped with a stirrer, a condenser and a thermometer, and 400 parts of carbitol acetate was added. The mixture was heated and dissolved, and methylhydroquinone 0.4 was added. 6 parts and 1.38 parts of triphenylphosphine were added, and the mixture was heated to 95 to 105 ° C., and 91 parts of acrylic acid was gradually dropped to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., and 159 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. In the reaction, the reaction solution is oxidized by potentiometric titration and total oxidation is measured. The reaction is followed at the obtained addition rate, and the reaction rate is determined to be 95% or more. The thus obtained carboxyl group-containing active energy ray-curable resin had a solid acid value of 98 mgKOH / g. Hereinafter, this reaction solution is referred to as A-3 varnish.
合成例 1 7  Synthesis Example 1 7
合成例 1 2で得られた反応生成物を、 8 0〜 9 0°Cまで冷却し、 テ トラヒ ドロフタル酸無水物 1 3 0部を加え、 8時間反応させた。 反応は、 電位差滴 定による反応液の酸化、 全酸化測定を行ない、 得られる付加率にて追跡し、 反応率 9 5 %以上を終点とする。 このようにして得られたカルボキシル基含 有活性エネルギー線硬化性樹脂は、 不揮発分 6 7 %、 固形物の酸価 1 0 2 m gKOHZgであった。 以下、 この反応溶液を A— 4ワニスと称す。  The reaction product obtained in Synthesis Example 12 was cooled to 80 to 90 ° C., and 130 parts of tetrahydrophthalic anhydride was added, followed by a reaction for 8 hours. The reaction is oxidized by potentiometric titration and the total oxidation is measured. The reaction is followed by the obtained addition rate, and the reaction rate is determined to be 95% or more as the end point. The carboxyl group-containing active energy ray-curable resin thus obtained had a nonvolatile content of 67% and an acid value of a solid of 102 mgKOHZg. Hereinafter, this reaction solution is referred to as A-4 varnish.
合成例 1 8  Synthesis Example 1 8
合成例 1 3で得られた反応生成物を、 8 0〜 9 0°Cまで冷却し、 テ トラヒ ドロフ夕ル酸無水物 1 3 0部を加え、 8時間反応させた。 反応は、 電位差滴 定による反応液の酸化、 全酸化測定を行ない、 得られる付加率にて追跡し、 反応率 9 5 %以上を終点とする。 このようにして得られたカルボキシル基含 有活性エネルギー線硬化性樹脂は、 不揮発分 6 7 %、 固形物の酸価 1 03 m gKOH /gであった。 以下、 この反応溶液を A— 5ワニスと称す。 The reaction product obtained in Synthesis Example 13 was cooled to 80 to 90 ° C., and 130 parts of tetrahydrofuroic anhydride was added and reacted for 8 hours. The reaction is oxidized by potentiometric titration and the total oxidation is measured. The reaction is followed by the obtained addition rate, and the reaction rate is determined to be 95% or more. The carboxyl group-containing active energy ray-curable resin thus obtained has a nonvolatile content of 67% and a solid acid value of 103 m. gKOH / g. Hereinafter, this reaction solution is referred to as A-5 varnish.
比較合成例 5  Comparative Synthesis Example 5
クレゾ一ルノボラック型ェポキシ樹脂 （ェピクロン N— 6 9 5、 大日本ィ ンキ化学工業 （株） 製、 エポキシ当量 2 2 0 g/e q. ) 3 3 0部を、 ガス 導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトー ルアセテート 4 0 0部を加え、 加熱溶解し、 ハイ ドロキノン 0. 4 6部と、 ト リフエニルホスフィ ン 1. 3 8部を加えた。 この混合物を 9 5〜 1 0 5 °C に加熱し、 アクリル酸 1 0 8部を徐々に滴下し、 1 6時間反応させた。 この 反応生成物を、 8 0〜 9 0 °Cまで冷却し、 テ トラヒ ド口フ夕ル酸無水物 1 6 3部を加え、 8時間反応させた。 反応は、 電位差滴定による反応液の酸化、 全酸化測定を行ない、 得られる付加率にて追跡し、 反応率 9 5 %以上を終点 とする。 このようにして得られたカルボキシル基含有感光性樹脂は、 固形物 の酸価 1 00 mg K 0 HZ であった。 以下、 この反応溶液を B— 1ワニス と称す。  Cresol novolak type epoxy resin (Epiclone N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 220 g / eq.) 330 parts of gas injection pipe, stirrer, cooling The mixture was placed in a flask equipped with a tube and a thermometer, 400 parts of carbitol acetate was added, and the mixture was dissolved by heating. 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C, and acrylic acid (108 parts) was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., added with 163 parts of tetrahydrofuric anhydride, and reacted for 8 hours. In the reaction, the reaction solution is oxidized by potentiometric titration and the total oxidation is measured. The reaction is followed by the obtained addition rate, and the reaction rate is 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a solid matter having an acid value of 100 mg K 0 HZ. Hereinafter, this reaction solution is referred to as B-1 varnish.
比較合成例 6  Comparative Synthesis Example 6
フエノールノボラヅク型エポキシ樹脂 （E P P N— 2 0 1、 日本化薬 （株） 製、 エポキシ当量 1 9 0 g/e q. ) 3 2 2部を、 ガス導入管、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビトールァセテ一ト 40 0 部を加え、 加熱溶解し、 ハイ ドロキノン 0. 4 6部と、 ト リフエニルホスフ イ ン 1. 38部を加えた。 この混合物を 9 5〜 1 0 5 °Cに加熱し、 アクリル 酸 1 2 2部を徐々に滴下し、 1 6時間反応させた。 この反応生成物を、 8 0 〜 9 0 °Cまで冷却し、 テトラヒ ド口フタル酸無水物 1 5 6部を加え、 8時間 反応させた。 反応は、 電位差滴定による反応液の酸化、 全酸化測定を行ない、 得られる付加率にて追跡し、 反応率 9 5 %以上を終点とする。 このようにし て得られたカルボキシル基含有感光性樹脂は、 固形物の酸価 9 6 mgK〇H / であった。 以下、 この反応溶液を B— 2ワニスと称す。  A phenol novolak type epoxy resin (EPPN-201, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 190 g / eq.) 32 2 parts of a gas introduction pipe, a stirrer, a cooling pipe and temperature In a flask equipped with a meter, 400 parts of carbitol acetate was added, and the mixture was dissolved by heating. 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C., and 122 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., and 156 parts of phthalic anhydride with tetrahydric acid was added, and the mixture was reacted for 8 hours. In the reaction, the reaction solution is oxidized by potentiometric titration and the total oxidation is measured. The reaction is followed by the obtained addition rate, and the reaction rate is determined to be 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a solid acid value of 96 mgK〇H /. Hereinafter, this reaction solution is referred to as B-2 varnish.
比較合成例 7  Comparative Synthesis Example 7
比較合成例 4で得られた多核エポキシ化合物 （h) 3 5 2部を、 撹拌装置、 冷却管及び温度計を備えたフラスコに入れ、 カルビト一ルァセテ一ト 400 部を加え、 加熱溶解し、 メチルハイ ドロキノン 0. 46部と、 ト リフエニル ホスフィン 1. 38部を加え、 95〜105。Cに加熱し、 アクリル酸 75部 を徐々に滴下し、 1 6時間反応させた。 この反応生成物を、 80〜90°Cま で冷却し、 テトラヒ ドロフ夕ル酸無水物 172部を加え、 8時間反応させた。 反応は、 電位差滴定による反応液の酸化、 全酸化測定を行ない、 得られる付 加率にて追跡し、 反応率 9 5 %以上を終点とする。 このようにして得られた カルボキシル基含有感光性樹脂は、 固形物の酸価 106mgKOHZgであ つた。 以下、 この反応溶液を B— 3ワニスと称す。 The polynuclear epoxy compound (h) 352 parts obtained in Comparative Synthesis Example 4 was stirred with a stirrer, Put into a flask equipped with a condenser and a thermometer, add 400 parts of carbitol acetate, heat and dissolve, add 0.46 parts of methylhydroquinone and 1.38 parts of triphenyl phosphine, and add 95 to 105 parts. The mixture was heated to C, and 75 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., and 172 parts of tetrahydrofuroic anhydride was added and reacted for 8 hours. In the reaction, the reaction solution is oxidized by potentiometric titration and the total oxidation is measured, and the reaction is followed by the obtained addition rate. The carboxyl group-containing photosensitive resin thus obtained had a solid acid value of 106 mgKOHZg. Hereinafter, this reaction solution is referred to as B-3 varnish.
実施例 14〜 1 8及び比較例 9〜； L 1  Examples 14 to 18 and Comparative Example 9; L 1
前記合成例 14〜 18及び比較合成例 5〜 7で得られた各ワニスを用いた 表 5に示す配合成分を、 3本口一ルミルで混練し、 光硬化性 .熱硬化性樹脂 組成物を得た。 各組成物の特性値を表 6に示す。  Using the varnishes obtained in Synthesis Examples 14 to 18 and Comparative Synthesis Examples 5 to 7, the components shown in Table 5 were kneaded in a three-hole mill, and a photocurable and thermosetting resin composition was obtained. Obtained. Table 6 shows the characteristic values of each composition.
表 5  Table 5
Figure imgf000057_0001
Figure imgf000057_0001
YX 4000 ： ビキシレノ一ル型エポキシ樹脂  YX 4000: Bixylene type epoxy resin
(ジャパンエポキシレジン （株） 製） 表 6 (Manufactured by Japan Epoxy Resin Co., Ltd.) Table 6
Figure imgf000058_0001
なお、 上記表 6中の性能試験の方法は以下の通りである。
Figure imgf000058_0001
The method of the performance test in Table 6 above is as follows.
<現像性> ：  <Developability>:
上記各実施例及び比較例の組成物を、 パターン形成された銅箔基板上にス クリーン印刷で全面塗布し、 80°Cで 40分、 50分、 60分、 又は 70分 乾燥し、 室温まで放冷した後、 30°Cの l %Na2C03水溶液をスプレー圧 2 k g/ cm2の条件で 60秒間現像を行ない、 乾燥塗膜の現像残りの有無 を目視で確認した。 判定基準は以下のとおりである 9 The composition of each of the above Examples and Comparative Examples was applied on the entire surface of the patterned copper foil substrate by screen printing, dried at 80 ° C for 40 minutes, 50 minutes, 60 minutes, or 70 minutes, and allowed to reach room temperature. after cooling, subjected to 60 seconds development of l% Na 2 C0 3 aqueous solution 30 ° C under the conditions of a spray pressure 2 kg / cm 2, to confirm the development remaining the presence of dried coating visually. The evaluation criteria are as follows 9
〇 ：完全に現像されている。  〇: Completely developed.
△ ：一部塗膜が残っている。  Δ: Part of the coating film remains.
X ：塗膜が完全に残っている。 <ガラス転移点 > ： X: The coating film is completely left. <Glass transition point>:
予め水洗 ·乾燥を行なったテフ口ン板に上記各実施例及び比較例の組成物 を、 スクリーン印刷法で塗布し、 熱風循環 ¾乾燥炉で 80°Cで 40分乾燥さ せた。 これを室温まで冷却した後、 露光量 50 OmJ/cm2の条件で露光 し、 熱風循環式乾燥炉で硬化を 150°Cで 60分間行なった。 これを'室温ま で冷却した後、 テフロン板から硬化塗膜をはがし、 評価サンプルを得た。 こ の評価サンプルのガラス転移点を DMA法により測定した。 The compositions of the above Examples and Comparative Examples were applied by screen printing to a Tef board that had been washed and dried in advance, and dried at 80 ° C. for 40 minutes in a hot air circulation drying oven. After cooling to room temperature, exposure was performed under the conditions of an exposure amount of 50 OmJ / cm 2 , and curing was performed at 150 ° C. for 60 minutes in a hot-air circulation drying oven. After cooling to room temperature, the cured coating film was peeled off from the Teflon plate to obtain an evaluation sample. The glass transition point of this evaluation sample was measured by the DMA method.
<引張弾性率、 引張強度 （引張破壊強さ） 、 伸び率 （引張破壊伸び） > ： 上記の評価サンプルの引張弾性率、 引張強度（引張破壊強さ）、 伸び率（引 張破壊伸び） を引張一圧縮試験機 （株式会社島津製作所製） によって測定し た。  <Tensile modulus, tensile strength (tensile breaking strength), elongation (tensile breaking elongation)>: The tensile elastic modulus, tensile strength (tensile breaking strength), and elongation (tensile breaking elongation) of the above evaluation sample It was measured by a tensile-compression tester (manufactured by Shimadzu Corporation).
<吸水率 > ：  <Water absorption>:
予め質量を測定したガラス板に上記各実施例及び比較例の組成物を、 スク リーン印刷法で塗布し、 熱風循璟式乾燥炉で 80°Cで 40分乾燥させた。 こ れを室温まで冷却した後、 露光量 500 m J/c m2の条件で露光し、 熱風 循環式乾燥炉で硬化を 150°Cで 60分間行ない、 評価サンプルを得た。 こ れを室温まで冷却した後、 評価サンプルの質量を測定した。 次に、 この評価 サンプルを P C T装置 （TABAI ESPEC HAST SYSTEM TPC-412MD) を用いて 1 2 1°C、 100%R. H. 、 24時間処理し、 処理後の硬化物の質量を測定し、 下記算式により硬化物の吸水率を求めた。 The compositions of the above Examples and Comparative Examples were applied to a glass plate whose mass was measured in advance by a screen printing method, and dried at 80 ° C. for 40 minutes in a hot air circulating drying oven. After cooling to room temperature, exposure was performed under the conditions of an exposure amount of 500 mJ / cm 2 , and curing was performed in a hot-air circulating drying oven at 150 ° C for 60 minutes to obtain an evaluation sample. After cooling to room temperature, the mass of the evaluation sample was measured. Next, this evaluation sample was treated using a PCT device (TABAI ESPEC HAST SYSTEM TPC-412MD) at 121 ° C, 100% RH for 24 hours, and the mass of the cured product after the treatment was measured. The water absorption of the cured product was determined.
吸水率 = (W2 -Wl ) / (W 1 -Wg)  Water absorption = (W2 -Wl) / (W 1 -Wg)
ここで、 W 1は評価サンプルの質量、 W 2は P C T処理後の評価サンプル の質量、 Wgはガラス板の質量である。  Here, W1 is the mass of the evaluation sample, W2 is the mass of the evaluation sample after the PCT treatment, and Wg is the mass of the glass plate.
<鉛筆硬度 > ： J I S K 5400に準拠して求めた。  <Pencil hardness>: Determined according to JIS K5400.
<密着性 > : J I S D 0202に準拠して目視判定した。 判定基準は 以下のとおりである。  <Adhesion>: Determined visually according to JISD0202. The criteria are as follows.
〇 ：全く剥がれが認められないもの  〇: No peeling is observed at all
△ ：ほんの僅か剥がれたもの X ：完全に剥がれたもの △: only slightly peeled X: Completely peeled
<電気絶縁性 > ：  <Electrical insulation>:
I P C B - 2 5のクシ型電極 Bクーポンに上記各実施例及び比較例の組 成物をパイロッ ト精ェ （株） 製ロールコ一夕一を用いて全面に塗布し、 熱風 循環式乾燥炉で 8 0°Cで 4 0分乾燥させた。 これを室温まで冷却した後、 露 光量 5 0 O mJZc m2の条件で露光し、 熱風循環式乾燥炉で硬化を 1 5 0°Cで 6 0分間行ない、 評価サンプルを得た。 このクシ型電極に D C 5 0 0 Vのバイァス電圧を印加し、 絶縁抵抗値を測定した。 The composition of each of the above Examples and Comparative Example was applied to the entire surface of the comb-type electrode B coupon of IPCB-25 using a roll iron manufactured by Pilot Seie Co., Ltd. Dried at 0 ° C for 40 minutes. This was cooled to room temperature, exposed with exposure light amount 5 0 O mJZc m 2 condition, the curing in a hot air circulating drying oven performs for 60 minutes at 1 5 0 ° C, to obtain an evaluation sample. A bias voltage of DC500 V was applied to this comb-shaped electrode, and the insulation resistance was measured.
<耐酸性試験 > ：  <Acid resistance test>:
電気絶縁性に用いたのと同じ評価基板を 1 0容量％硫酸水溶液に 2 0°Cで 3 0分間浸漬後取り出し、 塗膜の状態と密着性とを総合的に判定評価した。 判定基準は以下のとおりである。  The same evaluation substrate used for electrical insulation was immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C. for 30 minutes, taken out, and the state of the coating film and the adhesion were comprehensively evaluated. The criteria are as follows.
〇 ：変化が認められないもの  〇: No change is observed
Δ： ほんの僅か変化しているもの  Δ: a little change
X ：塗膜にフクレあるいは膨潤脱落があるもの  X: The coating film has blisters or swelling and falling off
く耐アル力リ性試験 > ： 1 0容量％硫酸水溶液を 1 0容量％水酸化ナトリ ゥム水溶液に変えた以外は耐酸性試験と同様に試験評価した。  The test was carried out in the same manner as in the acid resistance test except that the 10% by volume aqueous sulfuric acid solution was changed to a 10% by volume aqueous sodium hydroxide solution.
<P C T耐性 > ：  <PCT tolerance>:
プリント配線版に上記各実施例及び比較例の組成物を、 スクリーン印刷法 で塗布し、 熱風循環式乾燥炉で 8 0°Cで 4 0分乾燥させた。 これを室温まで 冷却した後、 露光量 5 0 Om J/cm2の条件で露光し、 熱風循環式乾燥炉 で硬化を 1 5 0°Cで 6 0分間行ない、 評価サンプルを得た。 これを室温まで 冷却した後、 P C T装置 （TABAI ESPEC HAST SYSTEM TPC-412MD) を用いて 1 2 1°C、 2気圧の条件で 1 6 8時間処理し、 硬化皮膜の状態を評価した。 判 定基準は以下のとおりである。 The compositions of the above Examples and Comparative Examples were applied to a printed wiring board by screen printing, and dried at 80 ° C. for 40 minutes in a hot-air circulation drying oven. After cooling to room temperature, exposure was performed under the conditions of an exposure amount of 50 Om J / cm 2 , and curing was performed in a hot-air circulating drying oven at 150 ° C. for 60 minutes to obtain an evaluation sample. After cooling to room temperature, it was treated with PCT equipment (TABAI ESPEC HAST SYSTEM TPC-412MD) at 121 ° C and 2 atm for 168 hours, and the state of the cured film was evaluated. The judgment criteria are as follows.
〇 ：剥がれ、 変色そして溶出なし。  ：: No peeling, discoloration and elution.
△ ：剥がれ、 変色そして溶出のいずれかあり。  Δ: Any of peeling, discoloration and elution.
X ：剥がれ、 変色そして溶出が多く見られる。 表 6に示す結果から明らかな如く、 本発明の光硬化性 ·熱硬化性樹脂組成 物から得られた硬化物は、 高いガラス転移点を有し、 機械的強度に優れ、 吸 水率、 密着性、 電気絶縁抵抗、 硬度、 耐桀品性、 P C T耐性等にも優れた特 性を有している。 これに対して、 比較例の芳香族エポキシァクリレート化合 物から得られた硬化物は、 ガラス転移点、 吸水率、 硬度、 P C T耐性等が劣 つていた。 産業上の利用可能性 X: Peeling, discoloration and elution are often observed. As is evident from the results shown in Table 6, the cured product obtained from the photocurable and thermosetting resin composition of the present invention has a high glass transition point, excellent mechanical strength, water absorption, and adhesion. It has excellent properties such as heat resistance, electrical insulation resistance, hardness, resistance to jealousy, and PCT resistance. On the other hand, the cured product obtained from the aromatic epoxy acrylate compound of Comparative Example was inferior in glass transition point, water absorption, hardness, PCT resistance and the like. Industrial applicability
本発明の多核エポキシ化合物は熱硬化可能であり、 また、 本発明の多核ェ ポキシァクリレ一ト化合物は、 活性エネルギー線の照射による硬化および熱 硬化のいずれも可能であり、 これらの硬化物は高いレベルで耐熱性と強靱性 のバランスがとれ、 基材に対する密着性に優れると共に、 耐水性、 耐薬品性、 電気絶縁性等に優れているので、 各種レジスト剤、 接着剤、 注型剤、 積層材、 塗料、 封止剤などの用途に有利に使用でき、 さらに本発明の活性エネルギー 線硬化性樹脂の出発原料として好適に用いることができる。  The polynuclear epoxy compound of the present invention is heat-curable, and the polynuclear epoxy acrylate compound of the present invention is capable of both curing by irradiation with active energy rays and thermal curing, and these cured products have high levels. The balance between heat resistance and toughness is excellent, and it has excellent adhesion to the base material, and is also excellent in water resistance, chemical resistance, electrical insulation, etc., so various resists, adhesives, casting agents, laminates It can be advantageously used for applications such as paints, sealants and the like, and can be suitably used as a starting material for the active energy ray-curable resin of the present invention.
また、 本発明の活性エネルギー線硬化性樹脂を光硬化性成分として含有す る本発明の光硬化性 ·熱硬化性樹脂組成物は、 光硬化性、 アルカリ現像性や 基材に対する密着性に優れると共に、 耐熱性、 耐水性、 耐無電解めつき性、 耐薬品性、 電気絶縁性、 フレキシブル性、 P C T耐性等に優れた硬化物が得 られるので、 上記のような用途の他に、 プリント配線板のソルダ一レジス ト や、 多層プリント配線板の層間絶縁層等として極めて有利に用いることがで ぎる 0 Further, the photocurable and thermosetting resin composition of the present invention containing the active energy ray-curable resin of the present invention as a photocurable component is excellent in photocurability, alkali developability and adhesion to a substrate. In addition, cured products with excellent heat resistance, water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexibility, PCT resistance, etc. can be obtained. solder one registry and a plate, in be used very advantageously as an interlayer insulating layer or the like of the multilayer printed wiring board Gill 0

Claims

請 求 の 範 囲 1. 下記一般式 （ 1) で表わされる多核エポキシ化合物,  Scope of Claim 1. Polynuclear epoxy compound represented by the following general formula (1),
0M 0M
H 2 1" •CHi -0— X— 0- H -CH— CH2一 0—Y— H 2 1 "• CHi -0— X— 0- H -CH— CH 2 0—Y—
\ /  \ /
0  0
0M  0M
■O—CEz— CH— CH2— 0— X— 0- - CH: (1) n 式中、 Xと Yは異なる芳香環を表わし、 Xはビフヱノール型ジグリシジル ェ一テル、 ビキシレノール型ジグリシジルェ一テル c、 ビスフエノール型ジグ ■ O—CEz— CH— CH 2 — 0— X— 0- -CH: (1) n In the formula, X and Y represent different aromatic rings, and X is biphenol-type diglycidyl ether and bixylenol-type diglycidyl ester. Ter c, bisphenol jig
\ H  \ H
リシジルエーテル及びナフ夕レン型ジグリシジルエー一 o Hテ \ cルよりなる群から選 Selected from the group consisting of glycidyl ether and naphthylene diglycidyl ether
H  H
ばれた少なくとも 1種の 1分子中に 2個のグリシジル基を有する芳香族ェポ キシ化合物の芳香環残基を表わし、 Υはジヒ ドロキシナフタレン及びその誘 導体、 ビフエノール及びその誘導体、 ビキシレノール及びその誘導体、 ビス フエノール及びその誘導体、 及びハイ ドロキノン及びその誘導体よりなる群 から選ばれた少なく とも 1種の 1分子中に 2個のフエノール性水酸基を有す る芳香族アルコールの芳香璟残基を表わし、 Μはグリシジル基及び/又は水 素原子を表わし、 ηは 1〜20の整数を表わす。 Represents an aromatic ring residue of an aromatic epoxy compound having two glycidyl groups in one molecule of at least one type, and Υ represents dihydroxynaphthalene and its derivative, biphenol and its derivative, bixylenol and The aromatic residue of an aromatic alcohol having at least two phenolic hydroxyl groups in one molecule of at least one selected from the group consisting of its derivatives, bisphenol and its derivatives, and hydroquinone and its derivatives Represents a glycidyl group and / or a hydrogen atom, and η represents an integer of 1 to 20.
2. 前記多核エポキシ化合物が、 下記一般式 （6) で表わされるェポキ シ化合物のアルコール性水酸基とェピハロヒ ドリン'とを反応させて得られた ものである請求項 1に記載の多核エポキシ化合物。  2. The polynuclear epoxy compound according to claim 1, wherein the polynuclear epoxy compound is obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (6) with epihalohydrin '.
0Η  0Η
CHZ-— CH— CH2— 0— X— 0 CH: -CH— CH2— 0— Y— 0— CH Z -— CH— CH 2 — 0— X— 0 CH : -CH— CH 2 — 0— Y— 0—
\ / L  \ / L
0  0
OH  OH
-CH2— CH— CH2—0— X (6)-CH 2 — CH— CH 2 —0— X (6)
Figure imgf000062_0001
式中、 Xと Yは異なる芳香璟を表わし、 Xはビフエノール型ジグリシジル エーテル、 ビキシレノール型ジグリシジルエーテル、 ビスフエノール型ジグ リシジルェ一テル及びナフ夕レン型ジグリシジルェ一テルよりなる群から選 ばれた少なく とも 1種の 1分子中に 2個のグリシジル基を有する芳香族ェポ キシ化合物の芳香環残基を表わし、 Υはジヒ ドロキシナフ夕レン及びその誘 導体、 ビフヱノール及びその誘導体、 ビキシレノール及びその誘導体、 ビス フエノ一ル及びその誘導体、 及びハイ ドロキノン及びその誘導体よりなる群 から選ばれた少なく とも 1種の 1分子中に 2個のフエノール性水酸基を有す る芳香族アルコールの芳香環残基を表わし、 ηは 1〜 2 0の整数を表わす。
Figure imgf000062_0001
In the formula, X and Y represent different aromatic groups, and X is at least one selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether. Each represents an aromatic ring residue of an aromatic epoxy compound having two glycidyl groups in one molecule, and Υ represents dihydroxynaphthylene and its derivative, biphenol and its derivative, and bixylenol and its derivative The aromatic ring residue of an aromatic alcohol having at least two phenolic hydroxyl groups in one molecule selected from the group consisting of phenol, bisphenol and its derivatives, and hydroquinone and its derivatives. And η represents an integer of 1 to 20.
3 . 下記一般式 （ 7 a ) で表わされるエポキシ化合物のアルコール性水 酸基とェピハロヒ ドリンとを反応させて得られる下記一般式 （ 8 a ) で表わ される多核エポキシ化合物。  3. A polynuclear epoxy compound represented by the following general formula (8a) obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (7a) with ephalohydrin.
a)
Figure imgf000063_0001
式中、 R 3、 R 4、 5 , R 6は同一の又は互いに異なる、 水素原子又は炭 素数 1〜4のアルキル基を表わし、 Mはグリシジル基及び/又は水素原子を 表わし、 nは 1〜2 0の整数を表わす。 a)
Figure imgf000063_0001
In the formula, R 3 , R 4 , 5 and R 6 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M represents a glycidyl group and / or a hydrogen atom, and n represents 1 to Represents an integer of 20.
4. 前記一般式 （7 a) 及び （8 a) において、 R 3〜： R 6が全て水素原 子である請求項 3に記載の多核エポキシ化合物。 4. The polynuclear epoxy compound according to claim 3, wherein in the general formulas (7a) and (8a), R 3 to R 6 are all hydrogen atoms.
5. 前記一般式 （ 7 a) 及び （8 a) において、 H3〜R6が全てメチル 基である請求項 3に記載の多核エポキシ化合物。 5. The polynuclear epoxy compound according to claim 3, wherein in the general formulas (7a) and (8a), H 3 to R 6 are all methyl groups.
6. 下記一般式 （7 b) で表わされるエポキシ化合物のアルコール性水 酸基とェピハロヒ ドリンとを反応させて得られる下記一般式 （8 b) で表わ される多核エポキシ化合物。  6. A polynuclear epoxy compound represented by the following general formula (8b) obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (7b) with ephalohydrin.
b)
Figure imgf000064_0001
5 b)
Figure imgf000064_0001
Five
C C
Figure imgf000064_0002
Figure imgf000064_0002
0M R' R R9 0M R 'RR 9
I I
CH2 -CH— CHS — 0- -C- -0- — CH2 -CH-CH2 (8b) CH 2 -CH— CH S — 0- -C- -0- — CH 2 -CH-CH 2 (8b)
I n \ / I n \ /
0 R' R10 0 0 R 'R 10 0
式中、 H7、 R8、 Rg、 R1 ()は同一の又は互いに異なる、 水素原子、 炭素 数 1〜4のアルキル基又はハロゲン原子を表わし、 I 11、 R12は同一の又 は互いに異なる、 水素原子、 メチル基又はハロゲン化メチル基を表わし、 M はグリシジル基及び/又は水素原子を表わし、 nは 1〜20の整数を表わす。 5In the formula, H 7 , R 8 , R g , and R 1 () are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and I 11 and R 12 are the same or different. Each represents a hydrogen atom, a methyl group or a halogenated methyl group, M represents a glycidyl group and / or a hydrogen atom, and n represents an integer of 1-20. Five
7. 前記一般式 （7 b) 及び （8 b) において、 R7〜： R1。が全て水素 原子であり、 R 1 1及び R 12が全てメチル基である請求項 6に記載の多核ェ ポキシ化合物。 7. In the general formulas (7b) and (8b), R 7 to: R 1 . 7. The polynuclear epoxy compound according to claim 6, wherein all are hydrogen atoms, and R 11 and R 12 are all methyl groups.
8. 前記一般式 （7 a) 、 （7 b) 、 （ 8 a) 及び （ 8 b) において、 二価のナフ夕レン環残基が 1 , 5—、 1 , 6—、 2， 6—又は 2 , 7—置換 体である請求項 3乃至 7のいずれか一項に記載の多核エポキシ化合物。 8. In the general formulas (7a), (7b), (8a) and (8b), 8. The polynuclear epoxy compound according to claim 3, wherein the divalent naphthylene ring residue is a 1,5-, 1,6-, 2,6- or 2,7-substituted product.
9. 請求項 1、 3又は 6に記載の多核エポキシ化合物と、 硬化剤を含有 する熱硬化性樹脂組成物。  9. A thermosetting resin composition comprising the polynuclear epoxy compound according to claim 1, 3 or 6, and a curing agent.
1 0. 下記一般式 （ 2 a)で示される多核エポキシァクリレート化合物。  10. Polynuclear epoxy acrylate compounds represented by the following general formula (2a).
0Ζ 0Ζ
Ζ' — 0— X— 0- ■CH2— CH— CH2— 0— Y— 0- Ζ '— 0— X— 0- ■ CH 2 — CH— CH 2 — 0— Y— 0-
OZ OZ
— CH2— CH— CH2— 0— X— 0- -Z' (2a) n 式中、 Xと Yは異なる芳香環を表わし、 Xはビフヱノ一ル型ジグリシジル ェ一テル、 ビキシレノール型ジグリシジルェ一テル、 ビスフエノール型ジグ リシジルェ一テル及びナフ夕レン型ジグリシジルエーテルよりなる群から選 ばれた少なく とも 1種の 1分子中に 2個のグリシジル基を有する芳香族ェポ キシ化合物の芳香環残基を表わし、 Υはジヒ ドロキシナフタレン及びその誘 導体、 ビフヱノール及びその誘導体、 ビキシレノ一ル及ぴその誘導体、 ビス フエノ一ル及びその誘導体、 及びハイ ドロキノン及びその誘導体よりなる群 から選ばれた少なぐとも 1種の 1分子中に 2個のフエノ一ル性水酸基を有す る芳香族アルコールの芳香環残基を表わし、 Ζは互いに無関係に、 下記一般 式 （ 3 ) もしくは （4) で示される基又は水素原子を表わし、 かつ Ζの少な く とも 1個は一般式 （ 3 ) で示される基であり、 Ζ， は互いに無関係に、 下 記一般式 （ 3， ) もしくは （ 4， ) で示される基を表わし、 ηは 1〜 2 0の 整数を表わす。 — CH 2 — CH— CH 2 — 0— X— 0- -Z '(2a) n In the formula, X and Y represent different aromatic rings, X is biphenyl-type diglycidyl ether, and bixylenol-type diglycidyl Aromatic ring of an aromatic epoxy compound having at least two glycidyl groups in one molecule selected from the group consisting of monoter, bisphenol type diglycidyl ether and naphthylene diglycidyl ether Represents a residue, and Υ is selected from the group consisting of dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bixylenol and its derivatives, bisphenol and its derivatives, and hydroquinone and its derivatives芳香 represents an aromatic ring residue of an aromatic alcohol having at least two phenolic hydroxyl groups in one molecule, and Ζ independently of each other, the following general formula (3) or Represents a group represented by (4) or a hydrogen atom, and at least one of Ζ is a group represented by the general formula (3), and Ζ and 互 い に independently of each other, the following general formula (3,) or Represents a group represented by (4,), and η represents an integer of 1 to 20.
R1 0 R1 R 1 0 R 1
一 I II 1  I I II 1
CH2 — C— CH2 -0-C-R2 … （3) — CH2一 C—— CH8 … （4)CH 2 — C— CH 2 -0-CR 2 … (3) — CH 2 one C—— CH 8 … (4)
I \ / I \ /
0H 0 0 0H 0 0
-CH2 -CH-CH2 一〇一 C一 R2 · ' ' (3' ) 一 CH2 — CH— CH2 (4' ) -CH 2 -CH-CH 2 1 1 C 1 R 2 · '' (3 ') 1 CH 2 — CH— CH 2 (4')
\ /  \ /
OH 0  OH 0
式中、 R1は水素原子又はメチル基を表わし、 R2は不飽和モノカルボン酸 残基を表わす。 In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an unsaturated monocarboxylic acid residue.
1 1. 下記一般式 （2 b)で示される多核エポキシァクリレート化合物。  1 1. A polynuclear epoxy acrylate compound represented by the following general formula (2b).
02  02
CH2— CH— CH2— 0— X— 0 CH2— CH— CH。一 0— Y— 0— CH 2 — CH— CH 2 — 0— X— 0 CH 2 — CH— CH. One 0— Y— 0—
\ / し  \ /
0  0
oz  oz
■CH2— CH— CH2—〇一 X— 0- — CH2— CH-CH: (2b) n \ / ■ CH 2 — CH— CH 2 —〇-1 X— 0- — CH 2 — CH-CH : (2b) n \ /
0 式中、 Xと Yは異なる芳香環を表わし、 Xはビフエノール型ジグリシジル ェ一テル、 ビキシレノール型ジグリシジルェ一テル、 ビスフエノール型ジグ リシジルエーテル及びナフ夕レン型ジグリシジルエーテルよりなる群から選 ばれた少なく とも 1種の 1分子中に 2個のグリシジル基を有する芳香族ェポ キシ化合物の芳香璟残基を表わし、 Υはジヒ ドロキシナフ夕レン及びその誘 導体、 ビフエノ一ル及びその誘導体、 ビキシレノール及びその誘導体、 ビス フエノール及びその誘導体、 及びハイ ドロキノン及びその誘導体よりなる群 から選ばれた少なく とも 1種の 1分子中に 2個のフエノール性水酸基を有す る芳香族アルコールの芳香環残基を表わし、 Ζは互いに無関係に、 下記一般 式 （3) もしくは （4) で示される基又は水素原子を表わし、 かつ Ζの少な く とも 1個は一般式 （3) で示される基であり、 ηは 1〜20の整数を表わ す。  In the formula, X and Y represent different aromatic rings, and X is selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthylene-type diglycidyl ether. Represents an aromatic residue of an aromatic epoxy compound having at least two glycidyl groups in one molecule, and 、 represents dihydroxynaphthylene and its derivative; biphenyl and its derivative; Aromatic ring of aromatic alcohol having at least two phenolic hydroxyl groups per molecule selected from the group consisting of bixylenol and its derivatives, bisphenol and its derivatives, and hydroquinone and its derivatives Represents a residue, Ζ represents a group represented by the following general formula (3) or (4) or a hydrogen atom, independently of each other. And, and one even least for the Ζ is a group represented by the general formula (3), eta is to Table Wa an integer of 1 to 20.
R1 0 R1 R 1 0 R 1
I II 1  I II 1
-CH2一 C— CH2 -0-C-R2 . . · (3) 一 CH2 — C—— CH2 . . . (4) -CH 2 one C- CH 2 -0-CR 2 · (3) one CH 2 -..... C-- CH 2 (4)
I \ /  I \ /
0H 0  0H 0
式中、 R1は水素原子又はメチル基を表わし、 H2は不飽和モノカルボン酸 残基を表わす。 In the formula, R 1 represents a hydrogen atom or a methyl group, and H 2 represents an unsaturated monocarboxylic acid Represents a residue.
12. 下記一般式（9 a)で示される多核エポキシァクリレ一ト化合物,  12. A polynuclear epoxy acrylate compound represented by the following general formula (9a),
Figure imgf000067_0001
Figure imgf000067_0001
式中、 R1は水素原子又はメチル基を表わし、 ： R2は不飽和モノカルボン酸 残基を表わす。 In the formula, R 1 represents a hydrogen atom or a methyl group, and: R 2 represents an unsaturated monocarboxylic acid residue.
13. 下記一般式 （ 9 b)で示される多核エポキシァクリレート化合物。  13. A polynuclear epoxy acrylate compound represented by the following general formula (9b).
Figure imgf000067_0002
式中、 R3、 R4、 R R6は同一の又は互いに異なる、 水素原子又は炭 素数 1〜4のアルキル基を表わし、 Zは互いに無関係に、 下記一般式 （ 3 ) もしくは （ 4 ) で示される基又は水素原子を表わし、 かつ Zの少なくとも 1 個は一般式 （ 3 ) で示される基であり、 nは 1 ~ 2 0の整数を表わす。
Figure imgf000067_0002
In the formula, R 3 , R 4 and RR 6 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is independently represented by the following general formula (3) or (4) And at least one of Z is a group represented by the general formula (3), and n represents an integer of 1 to 20.
— CH H2 · · ■ (4)
Figure imgf000068_0001
— CH H 2 · · (4)
Figure imgf000068_0001
式中、 R 1は水素原子又はメチル基を表わし、 R2は不飽和モノカルボン酸 残基を表わす。 In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an unsaturated monocarboxylic acid residue.
1 4. 前記一般式 （ 9 a) 又は （ 9 b) において、 R3〜R6が全て水素 原子である請求項 1 2又は 1 3に記載の多核エポキシァクリレート化合物。 1 4. In the general formula (9 a) or (9 b), polynuclear epoxy § chestnut rates compound according to claim 1 2 or 1 3 R 3 to R 6 are all hydrogen atoms.
1 5. 前記一般式 （ 9 a) 又は （ 9 b) において、 R 3〜： R 6が全てメチ ル基である請求項 1 2又は 1 3に記載の多核エポキシァクリレート化合物。 1 5. In the general formula (9 a) or (9 b), R 3 ~ : polynuclear epoxy § chestnut rates compound according to claim 1 2 or 1 3 R 6 are all methylation group.
1 6. 下記一般式（ 9 c ) で示される多核エポキシァクリレ一ト化合物。  1 6. A polynuclear epoxy acrylate compound represented by the following general formula (9c).
Figure imgf000068_0002
Figure imgf000068_0002
式中、 R R\ R \ R 1 C)は同一の又は互いに異なる、 水素原子、 炭素 数 1〜 4のアルキル基又はハロゲン原子を表わし、 1 1、 R 1 2は同一の又 は互いに異なる、 水素原子、 メチル基又はハロゲン化メチル基を表わし、 Z は互いに無関係に、 下記一般式 （ 3 ) もしくは （ 4) で示される基又は水素 原子を表わし、 かつ Zの少なく とも 1個は一般式（ 3 )で示される基であり、 Z 3 は互いに無関係に、 下記一般式 （3， ) もしくは （4， ) で示される基 を表わし、 nは 1〜 2 0の整数を表わす。 R1 0 R1 Wherein different RR \ R \ R 1 C) are identical or together, represent a hydrogen atom, an alkyl group or a halogen atom of from 1 to carbon atoms 4, 1 1, R 1 2 are different identical or another, hydrogen Z represents an atom, a methyl group or a methyl halide group, Z independently of each other, represents a group represented by the following general formula (3) or (4) or a hydrogen atom, and at least one of Z represents a group represented by the general formula (3) ), And Z 3 independently represents a group represented by the following general formula (3,) or (4,), and n represents an integer of 1 to 20. R 1 0 R 1
I II I  I II I
-CH2 -C-CH2一 0 - C一 R: (3) -CHi C— CH2 (4) -CH 2 -C-CH 2 1 0-C 1 R : (3) -CHi C— CH 2 (4)
\ /  \ /
OH 0  OH 0
0  0
-CHZ — CH— CH2 -0-C-R2 · (3， ) (4' ) -CH Z — CH— CH 2 -0-CR 2 · (3,) (4 ')
I I
OH OH
式中、 R1は水素原子又はメチル基を表わし、 R2は不飽和モノカルボン酸 残基を表わす。 In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an unsaturated monocarboxylic acid residue.
17. 前記一般式 （9 c) において、 R7~R 1 0が全て水素原子であり、 R11及び R12が全てメチル基である請求項 1 6に記載の多核エポキシァク リ レ一ト化合物。 17. The polynuclear epoxy acrylate compound according to claim 16, wherein in the general formula (9c), R 7 to R 10 are all hydrogen atoms, and R 11 and R 12 are all methyl groups.
18. 前記一般式 （ 9 a) 、 （ 9 b) 又は （ 9 c ) において、 二価のナ c  18. In the above general formula (9a), (9b) or (9c),
フタレン環残基が 1， 5—、 1 , 6—、 2, 6—又は 2, 7—置換体である 請求項 1 2、 13又は 1 6に記載の多核エポキシァクリ レート化合物。 The polynuclear epoxy acrylate compound according to claim 12, 13 or 16, wherein the phthalene ring residue is a 1,5-, 1,6-, 2,6- or 2,7-substituted product.
c c
\ H  \ H
19. 請求項 10、 1 1、 12、 13又は 1 6に記載の o多核エポキシァ 19. Polynuclear epoxyr according to claim 10, 11, 12, 13, or 16
/ c  / c
クリレート化合物と、 硬化剤及び/又は光重合開始剤を含有す Hる硬化性樹脂 組成物。 A curable resin composition comprising a acrylate compound and a curing agent and / or a photopolymerization initiator.
20. 下記一般式 （ 5 ) で示される多核エポキシ化合物 （a' ) と不飽 和基含有モノカルボン酸 （c) との反応生成物 （b， ) に、 多塩基酸無水物 (d) を反応させて得られる活性エネルギー線硬化性樹脂。  20. A polybasic acid anhydride (d) is added to a reaction product (b,) of a polynuclear epoxy compound (a ') represented by the following general formula (5) and a monocarboxylic acid containing an unsaturated group (c). Active energy ray-curable resin obtained by reaction.
0M. .  0M ...
CHi ■CH— CH2— 0— X' — 0- ■CH2— CH— CH2— 0— Y' — 0-CHi ■ CH— CH 2 — 0— X '— 0- ■ CH 2 — CH— CH 2 — 0— Y' — 0-
0 0
〇M  〇M
-CH2— CH— CH2—〇一 X' -0- -CH2— CH— CH: (5) n \ / -CH 2 — CH— CH 2 —〇 一 X '-0- -CH 2 — CH— CH: (5) n \ /
0  0
式中、 X5 と Y3 は互いに異なる 2価の芳香環を表わし、 Μはグリシジル 基及び/又は水素原子を表わし、 ηは 1〜20の整数を表わす。 In the formula, X 5 and Y 3 represent different divalent aromatic rings, Μ represents a glycidyl group and / or a hydrogen atom, and η represents an integer of 1 to 20.
2 1. (Α) 請求項 20に記載の活性エネルギー線硬化性樹脂、 （Β) 感光性 （メタ） ァクリレート化合物、 （C) 光重合開始剤、 及び （D) —分 子中に 2個以上のエポキシ基を有するエポキシ化合物を含有する、 アル力リ 水溶液により現像可能な光硬化性 ·熱硬化性樹脂組成物。 2 1. (Α) The active energy ray-curable resin according to claim 20, (Β) Photocurable, containing a (meth) acrylate compound, (C) a photopolymerization initiator, and (D) an epoxy compound having two or more epoxy groups in the molecule, which can be developed with an aqueous solution. · Thermosetting resin composition.
2 2. さらに （E) エポキシ硬化触媒を含有する請求項 2 1に記載の光 硬化性 ·熱硬化性樹脂組成物。  22. The photocurable and thermosetting resin composition according to claim 21, further comprising (E) an epoxy curing catalyst.
PCT/JP2001/000268 2000-01-18 2001-01-17 Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same WO2001053375A1 (en)

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JPWO2006004158A1 (en) * 2004-07-07 2008-04-24 太陽インキ製造株式会社 Photocurable / thermosetting resin composition, dry film using the same, and cured product thereof
JP4683182B2 (en) * 2004-09-28 2011-05-11 山栄化学株式会社 Photosensitive thermosetting resin composition, resist-coated printed wiring board and method for producing the same
JP4849860B2 (en) * 2005-10-04 2012-01-11 太陽ホールディングス株式会社 Photocurable / thermosetting resin composition, cured product thereof, and printed wiring board obtained using the same
JP5034939B2 (en) * 2005-10-27 2012-09-26 凸版印刷株式会社 Alkali-developable photosensitive resin composition, substrate with projections for controlling liquid crystal split alignment formed using the same, and liquid crystal display device
JPWO2013077307A1 (en) * 2011-11-22 2015-04-27 日本ペイントホールディングス株式会社 Hard coating composition
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