[go: up one dir, main page]

WO2001053375A1 - Compose epoxyde polynucleaire, resine durcissable par rayon energetique actinique obtenue a partir de ce compose, et composition de resine photodurcissable/thermodurcissable contenant ladite resine - Google Patents

Compose epoxyde polynucleaire, resine durcissable par rayon energetique actinique obtenue a partir de ce compose, et composition de resine photodurcissable/thermodurcissable contenant ladite resine Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
group
general formula
epoxy compound
polynuclear
epoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2001/000268
Other languages
English (en)
Japanese (ja)
Inventor
Noboru Kohiyama
Shoji Minegishi
Tadahiro Miyoshi
Hiromitsu Morino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2000090931A external-priority patent/JP3723036B2/ja
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Publication of WO2001053375A1 publication Critical patent/WO2001053375A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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

Landscapes

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

Abstract

L'invention concerne un composé époxyde polynucléaire linéaire comprenant des répétitions régulières de noyaux aromatiques de différentes sortes, en particulier un noyau à point de ramollissement élevé qui est un copolymère alternatif dans lequel un squelette biphényle ou biphénol et un squelette de naphtalène apparaissent alternativement. On obtient un composé d'acrylate époxyde polynucléaire linéaire en faisant réagir le composé époxyde polynucléaire avec un acide monocarboxylique possédant un groupe insaturé. On obtient, en outre une résine durcissable par rayon énergétique actif et soluble dans des solutions alcalines aqueuses par réaction du composé d'acrylate époxyde polynucléaire avec un anhydride d'acide polybasique. L'invention concerne également une composition de résine photodurcissable/thermoducissable développable aux alcalis, comprenant A) la résine durcissable par rayon énergétique actif, B) un composé de (méth)acrylate photosensible, C) un initiateur de photopolymérisation, et D) un composé époxyde polyfonctionnel.
PCT/JP2001/000268 2000-01-18 2001-01-17 Compose epoxyde polynucleaire, resine durcissable par rayon energetique actinique obtenue a partir de ce compose, et composition de resine photodurcissable/thermodurcissable contenant ladite resine Ceased WO2001053375A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2000008505 2000-01-18
JP2000-8505 2000-01-18
JP2000081036 2000-03-22
JP2000-81036 2000-03-22
JP2000090931A JP3723036B2 (ja) 2000-03-29 2000-03-29 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・熱硬化性樹脂組成物
JP2000-90931 2000-03-29

Publications (1)

Publication Number Publication Date
WO2001053375A1 true WO2001053375A1 (fr) 2001-07-26

Family

ID=27342072

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/000268 Ceased WO2001053375A1 (fr) 2000-01-18 2001-01-17 Compose epoxyde polynucleaire, resine durcissable par rayon energetique actinique obtenue a partir de ce compose, et composition de resine photodurcissable/thermodurcissable contenant ladite resine

Country Status (3)

Country Link
CN (1) CN1193056C (fr)
TW (1) TW524813B (fr)
WO (1) WO2001053375A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101591423B (zh) * 2008-05-29 2012-09-05 新日铁化学株式会社 碱可溶性树脂及其制造方法以及使用了碱可溶性树脂的感光性树脂组合物、固化物和滤色器

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100358932C (zh) * 2003-08-21 2008-01-02 旭化成化学株式会社 感光性组合物及其固化物
SG110189A1 (en) * 2003-09-26 2005-04-28 Japan Epoxy Resins Co Ltd Epoxy compound, preparation method thereof, and use thereof
KR100845657B1 (ko) * 2004-07-07 2008-07-10 다이요 잉키 세이조 가부시키가이샤 광 경화성·열 경화성 수지 조성물과 그것을 사용한 건식필름, 및 그의 경화물
JP4683182B2 (ja) * 2004-09-28 2011-05-11 山栄化学株式会社 感光性熱硬化性樹脂組成物、並びにレジスト被覆プリント配線板及びその製造法
JP4849860B2 (ja) * 2005-10-04 2012-01-11 太陽ホールディングス株式会社 光硬化性・熱硬化性樹脂組成物及びその硬化物並びにそれを用いて得られるプリント配線板
JP5034939B2 (ja) * 2005-10-27 2012-09-26 凸版印刷株式会社 アルカリ現像型感光性樹脂組成物、それを用いて形成した液晶分割配向制御用突起付き基板、及び液晶表示装置
CN104039903A (zh) * 2011-11-22 2014-09-10 日本油漆株式会社 硬涂层组合物
KR102541614B1 (ko) * 2015-03-04 2023-06-09 다이요 홀딩스 가부시키가이샤 에칭 레지스트 조성물 및 드라이 필름
JP6705412B2 (ja) * 2017-03-28 2020-06-03 味の素株式会社 感光性樹脂組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04353517A (ja) * 1991-05-31 1992-12-08 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物およびその硬化物
JPH0532764A (ja) * 1991-07-31 1993-02-09 Dainippon Ink & Chem Inc エポキシ樹脂組成物及びエポキシ樹脂の製造方法
US5948514A (en) * 1995-06-06 1999-09-07 Taiyo Ink Manufacturing Co., Ltd. Photocurable thermosettting resin composition developable with aqueous alkali solution

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04353517A (ja) * 1991-05-31 1992-12-08 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物およびその硬化物
JPH0532764A (ja) * 1991-07-31 1993-02-09 Dainippon Ink & Chem Inc エポキシ樹脂組成物及びエポキシ樹脂の製造方法
US5948514A (en) * 1995-06-06 1999-09-07 Taiyo Ink Manufacturing Co., Ltd. Photocurable thermosettting resin composition developable with aqueous alkali solution

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101591423B (zh) * 2008-05-29 2012-09-05 新日铁化学株式会社 碱可溶性树脂及其制造方法以及使用了碱可溶性树脂的感光性树脂组合物、固化物和滤色器

Also Published As

Publication number Publication date
CN1193056C (zh) 2005-03-16
CN1396937A (zh) 2003-02-12
TW524813B (en) 2003-03-21

Similar Documents

Publication Publication Date Title
JP3964326B2 (ja) カルボキシル基含有感光性樹脂、それを含有するアルカリ現像可能な光硬化性・熱硬化性組成物及びその硬化物
US20040067440A1 (en) Actinic energy ray-curable resin, photocurable and thermosetting resin composition containing the same, and cured products thereof
JP4087650B2 (ja) 光硬化性・熱硬化性樹脂組成物及びその硬化物
JP2001302871A (ja) 光硬化性・熱硬化性樹脂組成物とこれを用いて形成したソルダーレジスト皮膜や樹脂絶縁層を有するプリント配線板
US7718714B2 (en) Resin curable with actinic energy ray, photocurable and thermosetting resin composition containing the same, and cured product obtained therefrom
JP3953854B2 (ja) 光硬化性・熱硬化性樹脂組成物
JP4328593B2 (ja) カルボキシル基含有感光性樹脂を含有する組成物
JP3723036B2 (ja) 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・熱硬化性樹脂組成物
JP4713753B2 (ja) 光硬化性熱硬化性樹脂組成物及びその硬化物
WO2001053375A1 (fr) Compose epoxyde polynucleaire, resine durcissable par rayon energetique actinique obtenue a partir de ce compose, et composition de resine photodurcissable/thermodurcissable contenant ladite resine
JP3953852B2 (ja) 光硬化性・熱硬化性樹脂組成物
KR101394173B1 (ko) 강도, 경도 및 밀착성이 우수한 감광성 하이브리드 수지, 및 이것을 함유하는 알칼리현상이 가능한 경화성 조성물 및 그 경화물
JP2012017444A (ja) 硬化性樹脂組成物およびプリント配線板
JP3953851B2 (ja) 光硬化性・熱硬化性樹脂組成物
JP4840865B2 (ja) アルカリ現像可能な感光性樹脂組成物およびそれを用いたプリント配線板
JP4814134B2 (ja) 硬化性組成物及びその硬化物
JP3953853B2 (ja) 光硬化性・熱硬化性樹脂組成物
JP4713754B2 (ja) 光硬化性熱硬化性樹脂組成物及びその硬化物
JP5430884B2 (ja) アルカリ現像可能な硬化性組成物及びその硬化物
WO2003070800A1 (fr) Resine durcissable et composition contenant la resine durcissable
JP2007197530A (ja) 硬化性組成物及びその硬化物
JP2004359890A (ja) 光硬化性樹脂組成物及び感光性熱硬化性樹脂組成物並びにその硬化物
JPWO2005044777A1 (ja) テトラ（メタ）アクリレート化合物、それを含有する硬化性組成物及びそれらの硬化物
JP4814135B2 (ja) 硬化性組成物及びその硬化物
JP2008063452A (ja) 硬化性組成物及びその硬化物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN IN KR SG US VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 018038417

Country of ref document: CN

122 Ep: pct application non-entry in european phase