TW524813B - Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same - Google Patents

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

524813 A7 V. Description of the Invention (1) Technical Field of the Invention The present invention relates to linear novel multi-handed epoxy compounds containing regularly repeated dissimilar aromatic rings, and polynuclear propylene oxide derived from the multi-core epoxy compound. Acid ester compounds, and curable resin compositions containing the same. The present invention relates first to a linear active alkali-soluble novel linear energy-hardening resin derived from the above-mentioned polynuclear epoxy compound or polynuclear epoxy acrylate compound. Further, the present invention relates to a liquid'alkali developable photo-curable / thermosetting resin. Composition using the above-mentioned active energy ray-curable resin, and a hardened film formation technique using the same. The epoxy resin represented by the prior art bisphenol A epoxy resin has been widely used in adhesives, injection molding agents, and laminates due to its excellent adhesion, heat resistance, resistance to music, and electrical insulation. , Coatings, sealants and other uses. With regard to the epoxy resin, with recent developments in the electrical appliance and semiconductor industries, there is a demand for improvements in properties such as heat resistance, toughness, water resistance, and chemical resistance, and various novel epoxy compounds have been proposed to satisfy the related characteristics. 〇 For example, epoxy resins having excellent heat resistance include multi-core epoxy resins such as cresol lacquer type epoxy resin and phenol lacquer type epoxy resin. However, although some epoxy resins have excellent heat resistance, they have a large shrinkage during curing and a small stretch, and their toughness is not sufficient, and they have the disadvantage of easily cracking due to thermal shock. For this reason, in order to eliminate the above-mentioned shortcomings, epoxy resin is mixed with rubber components ^ ----- (Please read the precautions on the back before filling this page) The paper size printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Planning and Economics Applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -4 524813 A7 B7 V. Description of invention (2) (Please read the precautions on the back before filling in this page} Method (Japanese Patent Laid-Open Sho 6 3 — 1 9 9 2 1 8), a method of blending two kinds of epoxy resins (Japanese Patent No. 2 7 8 3 1 1 6) 'Copolymerized epoxy resin of biphenyl skeleton and bisphenol skeleton (Japanese patent No. 2789325), etc. However, with these methods, it is not currently possible to provide an epoxy compound that satisfies both heat resistance and temperature. On the other hand, known resins with excellent moldability such as hardenability and handleability are known. Free radicals such as bisphenol-type resins, lacquer-type epoxy resins and polyphenol-type epoxy resins and epoxy (meth) acrylic acid, acid esters, or unsaturated polyesters derived from (meth) acrylic acid Polymeric resins, these resins are usually formulated Combined with free-radical cross-linking agents such as styrene, they are widely used as vinyl ester resins or unsaturated polyester resins. However, these resins may not reach a satisfactory level in terms of thermal stability at high temperatures, and they shrink and stretch when hardened. Small, insufficient toughness, and shortcomings due to thermal shock. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed this. In order to eliminate the above shortcomings, there are modified aromatic amines, polymeric crosslinkers, and Resin composition composed of acryl fluorenyl and / or methacryl fluorinated butadiene acrylonitrile copolymer (Japanese Patent No. 2 5 3 9 8 7 3 chain) to modify aromatic polyamines and / or Proposed resin compositions (Japanese Patent Application Laid-Open No. Hei 1- 2 9 7 4 2 3) composed of high-quality aromatic diamines, epoxy compounds, and radical polymerizable cross-linking agents. However, these methods are in Toughness is still insufficient. Furthermore, the solder resist of some consumer printed circuit boards and almost all industrial printed circuit boards is from the point of view of high precision and high density. Yi Xian The image is formed by shadowing, and the paper size is determined by heat and light. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm)-5-524813 A7 _____B7 V. Description of the invention (3) Please fill in this page again for details) Liquid hardened solder resist that is finally hardened (formally hardened). From the consideration of environmental issues, use a dilute aqueous alkali solution for development. Liquid alkali developed hard solder resist has become mainstream. The alkali-developed liquid solder resist using a dilute aqueous alkali solution is, for example, the reaction product of a lacquer type epoxy compound disclosed in JP 6 1-2 4 3 8 6 9 and an unsaturated monobasic acid. It is a solder resist composition composed of a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy compound, and a lacquer-type epoxy compound disclosed in Japanese Patent Laid-Open No. 3-2 5 3 0 9 3 The reaction product of the saturated monobasic acid is added to the photosensitive resin with acid anhydride, and a photopolymerization initiator, a diluent, an ethylene triglyceride or an ethylene trio deer compound with dicyandiamide and a melamine resin. Revealed. However, although this type of photosensitive resin has excellent light-hardening properties and alkali developability, it is still difficult to say that the thermal stability at high temperatures has reached a satisfactory level, and it tends to shrink and harden when stretched. It has the disadvantage of cracking easily due to thermal shock. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. With the thinning and thinning of electronic equipment in recent years, corresponding to the increase in density of printed circuit boards, there is also a demand for higher performance of solder resist. And recently, so-called QFP (Quad Flat Package), SoP (Small Form Factor Package) IC packages that use lead frames and packaging resins have been replaced, and solder resist is applied to one side of the printed circuit board. Metals such as solder are arranged on the surface, and IC chips are directly connected by wire bonding or bumps on the other side, and then IC packages with resin encapsulation have appeared, so-called BGA (ball grid array package), CSP (chip size) Package) and so on. These packages are easier to count and miniaturize than Q F P packages of the same size. And this paper size applies the Zhongguanjia standard (CNS) A4 threat {210X297 mm) 7 ^ " 524813 A7 _ B7 V. Description of the invention (4), the self-alignment effect of the ball solder can be improved during construction. Rate has been quickly adopted. (Please read the precautions on the back before filling this page.) However, the printed circuit board using the conventionally available alkali-developed solder resist has a poor PCT resistance in the long-term reliability test of the package, and peeling of the solder resist film occurs. . In addition, due to the moisture absorption of the solder resist, the water absorbed inside the package boils during the reflow, and cracks occur in the film and surroundings of the solder resist in the package. The so-called popcorn phenomenon is a problem. The lack of moisture absorption and long-term reliability like this is not limited to the above-mentioned assembly technology, even in solder resists of general printed circuit boards, or interlayer insulation layers of multilayer circuit boards such as accumulation substrates; etc .; other uses The products do not want it to happen. Problems to be Solved by the Invention In view of the above-mentioned circumstances, one object of the present invention is to provide balanced heat resistance and toughness, and to have excellent adhesion to a substrate, water resistance, chemical resistance, electrical insulation, and the like. A polynuclear epoxy compound having good moldability, and a thermosetting resin composition containing the same. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, another purpose of the present invention is to provide a multi-core epoxy compound derived from a multi-core epoxy compound having excellent characteristics as described above, and irradiated with active energy rays for hardening and thermal curing An acrylate compound and a curable resin composition containing the same. Still another object of the present invention is to provide a flexible energy-curing resin which is excellent in thermal stability at high temperatures, has balanced heat resistance and toughness, and is excellent in both photo-hardening and alkali developability. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) ~ Γ ^ Τ 524813 A7 B7 V. Description of the invention (5) (Please read the precautions on the back before filling in this 苋) Another invention The purpose is to provide, maintain or improve the heat resistance, adhesion, electroless plating resistance, electrical characteristics, flexibility and other characteristics required for conventional solder resists of printed circuit boards and interlayer insulation layers of multilayer wiring boards. In addition, hardened films with excellent characteristics such as moisture absorption resistance and PCT (pressure cooker test) resistance required for I c packaging are available, and they are compatible with alkali-developable liquids for high density printed circuit boards and surface structure. Photocurable and thermosetting resin composition. In order to achieve the above-mentioned object by means of __, according to the first aspect of the present invention, a polynuclear epoxy compound (a) represented by the following general formula (1) and a thermosetting resin composition containing the same can be provided. . 0M,

-I CH2 -CH-CH2 -0-X-〇--CH2 -CH-CH2 -O-Y-

\ / L 〇

OM I 〇 一一 CH2 —CH-CH2-OX—0--CH2—CH—CH2 · · · (1) -n \ / 0 Economy, Ministry of Intellectual Property Bureau Employee Cooperative Cooperative Printing System, X and Y The different aromatic rings are shown, and the X is at least selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether. An aromatic ring residue of an aromatic epoxy compound having diglycidyl in one molecule, Y is selected from dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bixylenol and its derivatives, Bisphenol and its derivatives, and at least one aromatic ring residue of an aromatic alcohol having a diphenolic hydroxyl group in one molecule of a group of hydroquinone and its derivatives, where M represents an epoxy propyl group and a methyl propylene oxide group Dimensions are applicable to China National Standard (CNS) A4 specification < 210X297 mm) ~ TβZ '524813 A7 _________ B7_ 5. Description of the invention (6) Base and / or hydrogen atom, n is an integer from 1 to 20 in the table. As mentioned above, the polynuclear epoxy compound of the present invention is a linear polynuclear epoxy compound with different aromatic rings (especially high softening point biphenyls) because it contains regular repeats (please read the note on the back before filling this page). Cross-linked cross-linked linear polynuclear epoxy compound having a skeleton and a naphthalene skeleton, or an interpolymerization of a biphenol skeleton and a naphthalene skeleton. The hardened product of the polynuclear epoxy compound has a balanced high level of heat resistance and toughness. Excellent adhesion, excellent water resistance, chemical resistance, electrical insulation, etc. According to a second aspect of the present invention, a polynuclear epoxy acrylate compound (b) represented by the following general formula (2a) or (2b) and a thermosetting resin composition containing the same can be provided. ·

0Z

r I V -0-X—〇--ch2 —ch-ch2 -o-y-o- oz I Ί 一 CH2 —CH 一 CH2 " " * 〇kX 一 〇- ~ Z ’· · · (2a) oz

Γ I CH2 —CH—CH2 -o-x—ο--ch2 —ch-ch2 -o-y-o-

\ / L 〇oz Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I η ~ CH2 One CH—CH2 —0_? C_O -—— CH One CH2 And n are the same as above, Z is independent of each other, and the base or hydrogen atom represented by the following general formula (3) or. (4) is shown, and at least one of Z is the base represented by the general formula (3), Z ' They are independent of each other, and the bases shown in the following general formulae (3.) or (4,) are shown. This paper size is applicable to Mid-week National Standard (CNS) A4 specification (210X29 * 7mm) -9-524813 A7 B7 V. Description of invention (7) R1

-CH2 —0-CH2 -〇-C-R

0H

-CH2 »CH — CH2 — 〇— CR I 0H R1 (3) -CH2 -C · —CH2 \ / 0 (3) -CHa -CH-CH2 0 (4) (4,) where R1 represents a hydrogen atom Or the methyl, R2 unsaturated unsaturated monocarboxylic acid residues of the above-mentioned multi-core epoxy acrylate compound of the present invention can be hardened by the irradiation of active energy rays, or heat hardened, and its hardened products have a high level of heat resistance in balance. It has excellent toughness and toughness, excellent adhesion to the substrate, and excellent water resistance, chemical resistance, and electrical insulation. According to the third aspect of the present invention, the following general formula (5) can be provided (please read the precautions on the back before filling this page)

The reaction product (b ') of the polynuclear epoxy compound (a) shown by 0M is a reaction product (b') with a monocarboxylic acid (C) containing an unsaturated group and a polyacid anhydride (d). CHa —CH-CH2 —0—X * -0- CH2 -CH-CH2 -0-Yf -0- 〇 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 0M I -CH2 —CH—CH2 —0—X '1 0 · -CH ： -CH—CH: \ / 0 (5) In the formula, X 'and Y' represent different divalent aromatic rings, and M represents an epoxy group, a methyl epoxy group, and / or a hydrogen atom. Η is an integer of 1 to 20. According to the fourth aspect of the present invention, it can be provided, containing (.A) the above-mentioned active energy ray-curable resin, (B) a photosensitive (meth) propionate ester. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ·-524813 A7 _____B7_ V. Description of the invention (8) (Please read the notes on the back before filling this page) Compounds, (C) Photopolymerization start Initiator and (D) —Epoxy compounds with two or more epoxy groups in the molecule (hereinafter referred to as polyfunctional epoxy compounds) 'Photocuring and thermosetting properties that can be developed by aqueous alkaline solution The composition ratio of each component is not limited to a specific ratio, and (A) 100 parts by mass of the above active energy ray-curable resin, and (B) the above-mentioned photosensitive (meth) acrylate compound are preferably used in an amount of 10 to 60 parts by mass, preferably 15 to 50 parts by mass, (C) The above-mentioned photopolymerization initiator is preferably from 0.1 to 25 parts by weight, and more preferably from 0.5 to 20 parts by mass, (D ) The above-mentioned multifunctional epoxy compounds should be used in the range of 10 to 100. More than necessary (E) Epoxy curing catalyst should be used in the proportion of 0. 1 to 20. The Ministry of Economic Affairs Intellectual Property Bureau The consumer energy cooperative printed the active energy ray-curable resin of the present invention, because it is a linear polynuclear epoxy acrylate compound with regularly repeated different aromatic rings, especially a high-softening point biphenyl skeleton and a naphthalene skeleton, or biphenol Cross-copolymerized linear polynuclear epoxy acrylate compound of polybasic acid anhydride adduct of cross-copolymerization of skeleton and naphthalene skeleton, in addition to photo-hardening and alkali-solubility, excellent thermal stability at high temperature, balanced high-level heat resistance and Toughness. Also, with such active energy ray hardening The photocurable and thermosetting resin composition of the present invention, which is a photocurable component, is excellent in photocurability, alkali developability, and adhesion to a substrate, and has heat resistance, water resistance, and non-resistance. Hardened products with excellent electrolytic plating, chemical resistance, electrical insulation, flexibility, P c T resistance, etc. Brief illustration of the drawing Figure 1 shows the polynuclear epoxy compound (a-2) obtained in Synthesis Example 2. This paper size is in accordance with China National Standard (CNS) A4 specification (21〇 > < 297mm). ^ &Quot; 524813 A7 B7 V. Infrared absorption spectrum of invention description (9); Figure 2 is obtained from Synthesis Example 2 The nuclear magnetic resonance spectrum of the polynuclear epoxy compound (3-2); Figure 3 is the infrared absorption spectrum of the polynuclear epoxy acrylate compound (b-1) obtained in Synthesis Example 8; The nuclear magnetic resonance spectrum of the glycidyl epoxide compound (b-1); Figure 5. is the infrared absorption spectrum of the active energy ray hardening resin (A-1) obtained in Synthesis Example 14; and Figure 6 is the synthesis Of the active energy ray hardening resin (A-1) obtained in Example 14 Magnetic resonance spectra. The embodiment of the invention The inventors have repeatedly and carefully studied in order to achieve the above-mentioned purpose, and as a result, have found that the linear epoxy compounds including the aromatic rings represented by the above-mentioned X and Y which are repeated repeatedly, especially the biphenyl skeleton with a high softening point and A polynuclear epoxy compound obtained by the reaction of an alcoholic hydroxyl group in a copolymerized linear epoxy compound in which a naphthalene skeleton or a bisphenol skeleton and a naphthalene skeleton are co-polymerized, and a halogenated propylene oxide reaction can result in both excellent heat resistance and toughness. Of hardened. That is, the polynuclear epoxy compound (a) of the present invention, as shown in the following general formula (1), contains regularly repeated different aromatic rings, can obtain a hardened product with high mechanical strength, and because of its linear structure, In addition, the polynuclear epoxy compound obtained by the reaction with epihalohydrin can obtain hardened products with high heat resistance, and at the same time can obtain the adhesion to the substrate, water resistance, chemical resistance, electrical insulation, and cost. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm). 12- (Please read the notes on the back before filling out this page) • Binding and printing printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative 524813 A7 B7_____ V. Description of the invention (1〇) Hardened materials with excellent formability

0M

-I CH2 -CH-CH2 —0-X—0--CH2 -CH-CH2 -0-Y- (Please read the precautions on the back before filling this page)

\ / L 〇

0M I _ 1 0—CH2 —CH—CH2—0—X—0—CHs —CH—CH8 Diepoxy is present in at least one of the groups of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether. Aryl ring residues of propyl aromatic epoxy compounds, γ 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 have at least one group of diphenols. The aromatic ring residues of aromatic alcohols of the formula hydroxy, M represents an epoxy propyl group, a methyl epoxy propyl group and / or a hydrogen atom, η is an integer from 1 to 20. The above-mentioned polynuclear epoxy compound can be produced by various methods, and especially the polyhydric epoxy compound obtained by reacting the alcoholic hydroxyl group of the epoxy compound represented by the following general formula (6) with epihalohydrin is preferred, Easy to manufacture. 0Η Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Γ | CH2 —CH—CH2 —ο--CHa —CH—CH2 —0—Y—〇

Χ / L 〇

OH I Ί ~ CH2 -CH-CH2 -0-x-o--GH2 -CH-CH2 (6) J n \ / where X, Y, and n are the same as above. ο A more specific suitable aspect is the reaction between the alcoholic hydroxyl group of the epoxy compound represented by the general formula (7 a.) or (7 b) below and the epoxy halopropane. ) A4 specification (210 father 297 mm 1 -13- 524813 A7 B7 V. Description of the invention (11

Remarks ~ R3 / R6 t C 表 as shown in the general formula (8 a) or (8 b): \ 2 ~ CH—CH / 2 1 $ > < x —0— —CHa 0 R4, Re 0H R3 R5 0H I -CH2 _CH ~ CHa 10— CH2 — CH—CH2 —0

R7 R11 R9 k I CH2 One CH-CHa -0 ~ of 〇 0 R8 R12 R10 0H CHa -CH-CH2 -0- (Please read the precautions on the back first and fill in this page) -Installation · 〇

• CH—CH * · · · (7b) / 0M 0 4 I • CH * -CH-CH2 —〇—〇- \ / 0 Order (8 a)

CH2 —CH—CH2 n \ / OM CΗ2 —CH—CΗ2 — 0- R8 R12 H10 0 In the formula, R3, R 4 R5, r6 represent the same or different hydrogen atoms or CHa -CH-CH2 -〇-0- (8b) an alkyl group having 1 to 4 carbon atoms, R 7, R 8, R 9, R 1. Table of the same or different hydrogen atoms or different hydrogen atoms, the number of carbon atoms 1 to 4, the basis of this paper applies the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -14-524813 A7 B7_ 5 2. Description of the invention (12) (Please read the notes on the back before filling this page) or halogen atom, Rll, R ^ 2 are the same or different hydrogen atom, methyl group or halogenated methyl group, M means epoxypropyl group, Methylglycidyl and / or hydrogen atom, η is an integer of 1 to 20 in Tables. Among the epoxy compounds represented by the general formulae (7a), (7b), (8a), and (8b) in a suitable aspect, all of R 3 to R 6 are hydrogen atoms or all of R 3 to R 6 are methyl groups, And R7 to R1Q are all hydrogen atoms, and R11 and R12 are all methyl groups. On the other hand, the divalent naphthalene ring residue is 1, 5 —, 1 '6-, 2, 6-, or 2, 7 — Substitute. In a particularly suitable form, all of the above R 3 to R 6 are radicals, and the above-mentioned divalent naphthalene ring residual group is a 1,5 —, 1, 6 —, or 2, Θ — substituent. In addition, the epoxy compound represented by the above general formula (6) decreases the epoxidation yield of epoxy halopropane as the number average molecular weight increases, and the present invention uses this to adjust the alkali metal hydrogen as a catalyst. The amount of oxide can also epoxidize the alcoholic hydroxyl group at a desired ratio. Hereinafter, the polynuclear epoxy compound of the present invention will be described in detail. First, the epoxy compound represented by the general formula (6), (7a) or (7b) will be described. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the epoxy compound represented by the above general formula (6). An aromatic epoxy compound (hereinafter referred to as a bifunctional aromatic cyclic epoxy compound) having diglycidyl group in one molecule can be used. ), And an aromatic alcohol with a diphenolic hydroxyl group in one molecule (hereinafter referred to as a difunctional aromatic alcohol) as a raw material, using a known esterification catalyst as described below, in a solvent or without a solvent, interactive polymerization is simple and convenient Manufacturing. The above-mentioned difunctional aromatic epoxy compounds are applicable to those selected from the group consisting of bisphenol-type dipropylene oxide ethers having aromatic rings as shown in the following formulae (A) to (D), and the size of the paper is subject to Chinese national standards ( CNS) A4 specification (210X297 mm) -15-524813 A7 V. Description of the invention (13) (Please read the precautions on the back before filling out this page} Cresol dipropylene oxide, bisphenol dipropylene oxide Ether and naphthalene-type dipropylene oxide ether group of at least one difunctional aromatic epoxy compound. With such a difunctional aromatic epoxy compound 'and a difunctional aromatic alcohol cross-copolymerization, the strength of the hardened material can be obtained Polynuclear epoxy compounds with excellent heat resistance, electrical insulation, etc.

_Q_s〇2 ^ Qk- (C) (D) In the formula, R3, R4, R5, R6 represent the same or different hydrogen atom or alkyl group having 1 to 4 carbon atoms' R 7, R 8, R 9, R 1 Q represents the same or different hydrogen atom, alkyl group or halogen atom having 1 to 4 carbon atoms' R 11, R 12 represents the same or different hydrogen atom, methyl group or halogenated methyl group. The above-mentioned biphenol-type, bixylenol-type, bisphenol-type or naphthalene-type diglycidyl ether is printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and can be used for example by biphenol compounds, bixyphenol compounds, bisphenol compounds, or Dihydroxynaphthalene, produced by the reaction with epihalohydrin. Also, a “commercially available epoxy compound” may be used, for example, “Epicote YL — 6 0 5 6”, a brand name of “Epiote YL — 6 0 5 6” made of Bisphenol-type dipropylene oxide ether. Cresol type diglycidyl ether made by Japan Epoxy Resin Co., Ltd. under the trade name "Ep1C〇te YX-4 0 0", etc., bisphenol type diglycidyl ether manufactured by Asahi Kasei Epoxy Co., Ltd. Product names "Araldite # 260", "Araldite # 607 1" and other bisphenol A epoxy compounds, or Dainippon Ink Chemical Co., Ltd. Paper size applies Chinese National Standard (CNS) A4 specifications (210 X297 mm) -16 -Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524813 A7 B7 ___ V. Description of the invention (14) Bisphenol ^^ epoxy compounds such as the trade name "Epklon 830S", or Dainippon Ink Chemistry Industrial products (Epiclon EXA15 14) and other bisphenol S-type epoxy compounds, etc., naphthalene-type dipropylene oxide ether, and product names "Epic Ion HP — 40" 3 2 (D) ", etc. These can be used alone or in combination of two or more. The bifunctional aromatic alcohol used in the present invention has a structural feature, an aromatic ring capable of improving heat resistance, and can be used for symmetrical structure or rigid structure. Examples of such a compound include 1,4-dihydroxynaphthalene, .1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2 Dihydroxy naphthalene derivatives such as 8-dihydroxynaphthalene, biphenol derivatives, biphenol derivatives, biphenol derivatives, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted bisphenol derivatives, etc. Derivatives, hydroquinone, methylhydroquinone, trimethylhydroquinone, etc. These can be used alone or in combination of two or more. Among the epoxy compounds represented by the general formula (6), the general formula The epoxy compound represented by (7a) or (7b) is preferred. The epoxy compound represented by the general formula (7a) or (7b) may be a biphenyl-type and / or bixylenol-type epoxy compound or a bisphenol-type epoxy compound, and 1, 5, 1, 1, At least one dihydroxynaphthalene such as 6-, 2,6-, 2,7-substituent and the like is used as a raw material, and is easily produced by an etherification catalyst, in a solvent or solvent-free cross-polymerization. The dihydroxynaphthalene is preferably a 1,5-, 1 '6-or 2,6 -substituent having a high softening point, and particularly a symmetrical 1,5-and 2,6 -substituent. This paper size applies Chinese National Standard (CNS) (210X297 male) 1 ^ | 7-'~ " I ---- · ---------, 玎 ------ 0r (Please (Please read the precautions on the back before filling this page) 524813 A7 __B7 V. Description of the invention (5) is used for the rings of the above general formulae (6) and (7a), (7b) (please read the notes on the back first) Please fill in this page for more details.) The catalyst for the synthesis of oxygen compounds is preferably used alone or in combination with phosphine, alkali metal compounds, and amines based on the quantitative reaction of glycidyl group and hydrazone formula. Other catalysts are not good because of gelation. Examples of the phosphines include trialkylphosphine or triarylphosphine such as tributylphosphine and triphenylphosphine, or salts thereof with oxygen compounds. Examples of the alkali metal compound include hydroxides, halides, alcoholates, and amidines of alkali metals such as sodium, lithium, and potassium. These may be used alone or in combination of two or more. Examples of the amines include aliphatic, aromatic one-, two-, three-, and four-stage amines, and these may be used alone or in combination of two or more. Specific examples of the amines include triethanolamine, N, N-dimethylpiperazine, diethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, and tetramethylammonium bromide. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints these catalysts, with respect to the above-mentioned total amount of the difunctional aromatic epoxy compound and difunctional aromatic alcohol of 100 parts by mass, in order to use 0.001 to 1 Part by mass is preferable, and 0.01 to 1 part by mass is more preferable. The reason is that if the amount of catalyst used is less than 0.01 parts by mass, the time required should be uneconomical. 'On the other hand, if it exceeds 1 part by mass, the reaction is too fast and difficult to control. In addition, the reaction between a difunctional aromatic epoxy compound and a difunctional aromatic alcohol is in the temperature range of 130 to 180 ° C in an inert gas stream or in the air in the presence of the above catalyst. Better to proceed. Next, the polynuclear epoxy compound of the present invention represented by the general formulae (1), (8a), and (8b) will be described. The paper size shown in the general formulae (1) or (8a) and (8b) above is applicable to China National Standards (CNS) A4 specifications (210X297 mm) -18-524813 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation A7 _B7 V. Description of the invention (16) The polynuclear epoxy compound described in (16) can be used in a known solvent as described below or in the absence of a solvent in the presence of an alkali metal hydroxide using the general formula (6) or ( 7a) and (7b) are produced by reacting an alcoholic hydroxyl group with an epoxy halopropane. The epihalohydrin can be used, for example, epichlorohydrin, epibromopropane, iodopropane, / 5-methylepoxychloropropane, / 3-methylepoxybromopropane, / 5-methylcyclopropane Oxyiodopropane and the like. In the polynuclear epoxy compound of the present invention represented by the general formulae (1), (8a), and (8b), the amount of epihalohydrin used is relative to the general formulae (6) or (7a), X 7 b 1 equivalent of the alcoholic hydroxyl group is preferably 0.1 times equivalent. However, if it is more than 15 times equivalent to 1 equivalent of the above-mentioned hydroxyl group, the volumetric efficiency is poor and unsatisfactory. As the solvent, known are aprotic polar solvents such as dimethylarylene, N, N-dimethylformamide, N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene. Solvents, among which aprotic polar solvents, especially dimethyl arylene, are preferred. The solvent is preferably used in an amount of 5 to 300% by mass based on the epoxy compound represented by the general formulae (6) or (7a) and (7b). The reason is that if the content is less than 5% by mass, the reaction between the alcoholic hydroxyl group and the epihalohydrin is slow. On the other hand, if the content exceeds 300% by mass, the volumetric efficiency is deteriorated. As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide, potassium hydroxide, calcium hydroxide and the like can be used, and sodium hydroxide is particularly preferred. The alkali metal hydroxide is used in an amount of 1 equivalent to the alcoholic hydroxyl group to be epoxidized in the epoxy compound represented by the general formulae (6) or (7a) and (7b). Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -19-----.--- ^ ------ IT ------ " (Please read the notes on the back first Fill out this page again) 524813 A7 B7 V. Description of the invention (17) to 2 times the equivalent is better. Epoxy represented by the above general formula (6) or (7a), (7b) (please read the precautions on the back first) (Fill in this page) The reaction temperature of the alcoholic hydroxy group and the epihalohydrin in the compound is preferably above 20 ° C, preferably above 30 ° C, and preferably below 100 ° C. The reason is In other words, if the reaction temperature is lower than 20 ° C, the reaction is slow and the time required for the reaction is long. On the other hand, if the reaction temperature exceeds 100 t, side reactions often occur and are not good. The above general formula (6) Or (7a), (7b) the alcoholic hydroxyl groups in the epoxy compounds shown in the table and the epoxy halopropane reaction, can be used in quaternary ammonium salt or quaternary ammonium salt, etc. , The coexistence of 3-dimethyl-2-imidazoline and an alkali metal hydroxide is carried out by adjusting the amount of the alkali metal hydroxide. At this time, the solvent may be an alcohol such as methanol or ethanol, or toluene Aromatic hydrocarbons such as xylene, ketones such as methyl isobutyl methanol and methyl ethyl ketone, cyclic ether compounds such as tetrahydrofuran, etc. Printed and available for use by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Specific examples of the quaternary basic salt compound include, for example, tetramethylammonium chloride, tetrabutylammonium bromide, trimethyltolylammonium halide, tetramethylammonium bicarbonate, tetramethylammonium benzoate, and tetrahydroxide. Methylammonium, tetraethylammonium hydroxide, tetramethyl iron hydroxide, etc. The catalyst can be used singly or in combination of two or more. The amount used is based on the above general formula (6) or (7a), (7b). The epoxy group has 1 equivalent of the hydroxyl group, preferably in the range of 0 to 0. 0 to 1 equivalent. More preferably, it is in the range of 0 to 0.5 to 2 equivalents. The effect is less than 0 to 0 to 1 equivalent. It is obvious, and the propylene oxide ether group of the raw material epoxy compound reacts with the hydroxyl group of the epoxy compound to be high Molecular weight, it is not good. On the other hand, when adding more than 2 equivalents, the effect of the standard paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm)-20- 524813 A7 ---- — _ B7 ___ V. Description of the invention (18) Outside promotion (Please read the notes on the back before filling this page) The polynuclear epoxy compound of the present invention, which can be prepared in this way, has a number average molecular weight of 400 to 5000, It is preferably 500 to 3000, and more preferably 500 to 2000. When the number-average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is insufficient. On the other hand, when it exceeds 5000 ', the solubility of the solvent is reduced and it is not good. The epoxidation rate can be appropriately selected according to the purpose (depending on the required physical properties), 10 to 100% is appropriate, 30 to 90% is preferable, and 4 to 80% is more preferable. The polynuclear epoxy compound of the present invention can be used alone or in combination with other epoxy resins. Like ordinary epoxy resins, a hardener can be added, and if necessary, a hardening accelerator can be used to harden. As the epoxy resin, various conventionally known epoxy resins (D) exemplified below can be used alone or in combination of two or more. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics The hardener used can be amine compounds, acid anhydride compounds, amidine compounds, phenol compounds, etc. Specific examples include the synthesis of diamine diphenylmethane, diethylenetriamine, diaminodiphenyl master, isophorone diamine, dicyandiamide, linolein dimer and ethylenediamine Polyamine resin, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, tetrayltetrahydrophthalic anhydride, methylnorbornene anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenolic lacquer , And these modified products, imidazole, BF 3 -amine complex, guanidine derivatives and the like. These hardeners can be used individually or in combination of two or more. Hardening accelerators can be, for example, imidazoles, tertiary amines, phenols, and gold paper. Applicable to China National Standard (CNS) A4 specifications (210X29 * 7 mm) -21-Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed 524813 A 7 ___B7_ V. Description of the invention (19)) I ill compound, etc. In this way, the polynuclear epoxy compound, hardener, hardening accelerator, etc. of the present invention is an epoxy resin composition 'The hardened | cured material of an epoxy resin composition can be manufactured easily under the same conditions as a conventionally known method. For example, the polynuclear epoxy compound, hardener, filler, and other additives of the present invention are mixed, and if necessary, thoroughly mixed with an extruder, kneader, or roller to obtain an epoxy resin composition 5 After the composition is melted, it is formed by injection molding or transfer molding, and then heated at 80 to 200 t to obtain a hardened product. In addition, the epoxy resin composition is dissolved in a solvent, impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other substrates, and dried by heating to obtain a film, and a hardened product can also be obtained by hot pressing. . In addition, various additives such as inorganic fillers and organic fillers may be added to the epoxy resin composition as necessary. The resin composition made of the multi-core epoxy compound, the hardener, and the hardening accelerator when necessary can be dissolved in a solvent and adjusted to a viscosity suitable for the coating method. Examples of such solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetra toluene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and methylformate. Glycolol, butylcarbitol, propylene glycol monomethanol, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, cellosolve acetate Acetates such as cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethanol acetate, dipropylene glycol monomethyl ether acetate, etc .; ethanol, propanol, ethylene glycol Alcohols such as propylene glycol and propylene glycol; octane and decane paper standards are applicable to China National Standards (CNS) Ya 4 threats (210X 297 public holidays) = 22-one IT (Please read the precautions on the back before filling this page) 524813 A7 ___ B7 V. Description of the invention (20) Ester hydrocarbons such as alkanes; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent light oil, etc. These organic solvents can be used singly or in combination of two or more kinds. According to the research conducted by the inventors, it is found that the linear polynuclear epoxy compound as described above, especially a high-softening point biphenyl skeleton and a naphthalene skeleton, or an interactive copolymerization type of a linear copolymerization of a bisphenol skeleton and a naphthalene skeleton. The polynuclear epoxy compound 'is obtained by reacting an unsaturated monobasic acid (C) with a polynuclear epoxy acrylate compound (b) represented by the following general formula (2a) or (2b), which can be photo-hardened or Heat hardening, and because of this hardening treatment, it can lead to hardened products with excellent heat resistance and toughness. ’Z’-0—X—〇— 0Z I CH2—CH—CH2 ~ 0—Y —〇— 0Z I—d — CH—CH2 — 0— 一 〇-

0Z -Z, (2a) CH2 —CH—CH2 —0— X — 〇- 〇

0Z I _CH2 —CH—CH2 — 0—Y—〇— -----.-------------- IT ------ 0 (Please read the precautions on the back first (Refill this page) -CHa —CH-CHj (2b) printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, where X and Y are different aromatic rings, and X is selected from biphenol-type dipropylene oxide, Aryl ring of at least one aromatic epoxy compound having diglycidyl group in one molecule of at least one group formed by xylenol type diglycidyl ether, bisphenol type diglycidyl ether, and naphthalene type diglycidyl ether Residual and Y are selected from dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bixylenol and its derivatives, bisphenol and its derivatives. The paper size applies to Chinese National Standard (CNS) A4 specifications. (210X297 mm) -23 524813 A 7 B7 V. Description of the invention (21) and at least one of the groups of qiku and its derivatives are aromatic ring residues of aromatic alcohols with difluorene hydroxyl groups in one molecule. The base and z are independent of each other. The following table is general (please read the notes on the back before filling this page) The base or hydrogen atom shown by formula (3) or (4), and at least one of Z is the general formula ( 3) The base shown, Z 'is independent of each other The bases shown in the following general formulae (3 ') or (4') are shown, and η is an integer from 1 to 20. R1 0 R1

I II I -CH2 -C-CH2 -0-C-R2 · · · (3) — CH2 -C ——CH2 · · · (4) I \ / OH 0

0 II a CH2 — CH — CH2 —0 — C-R2 · · · (3,) -CH2 -CH-CHa · · · (4,) I \ / OH R2 represents unsaturated monobasic acid residues. 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. That is, the multi-core epoxy acrylate compound (b) of the present invention contains the above-mentioned general formula (2a) or (2) b) The different aromatic rings shown are hardened products with high mechanical strength, and because of the linear structure, and because of the reaction of unsaturated monobasic acids with polynuclear epoxy compounds, they can be hardened by light or heat. A hardened product having high heat resistance and a hardened product having excellent adhesion to a substrate, water resistance, chemical resistance, electrical insulation, and formability can be obtained. A more specific suitable aspect is a polynuclear epoxy acrylate compound represented by the following general formulae (9a) to (9d). This paper size applies to Chinese national standard (CNS> A4 specification (210 X 297 mm) -24-524813 A7 B7 V. Description of the invention (22 R8 Z, 1〇

0Z CΗ2 —CH—CΗ2 — 0—〇— 0Z I—CH2 — CH—CH2 — 0

(9a) R3 R6.

One CH2 one CH one CH2 one 0

0Z -CHa --CH-CΗ2 -0——〇-

CH2 -CH—CHa n \ / 0 (9b) (Please read the precautions on the back before filling this page)

R7 R11 R9 〇Z

In the printed format of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, R3 to R12, Z and n are the same as above. In a suitable state, either R 3 to R 6 are all hydrogen atoms, or R 3 to R 6 are all methyl groups, and R 7 to R 1 Q are all hydrogen atoms. R 11 and R 12 are all paper sizes. The national paper standards are applicable to Chinese standards. (CNS) A4 specification (210 X297 mm) -25-524813 A7 B7 V. Description of the invention (23) group, on the other hand, the divalent naphthalene ring residual group is 1, 5 —, 1, 6 —, (please Read the notes on the back before filling out this page) 2, 6-, or 2, 7 —substitute. In a particularly suitable aspect, the aforementioned R 3 to R 6 are all methyl groups, and the aforementioned divalent naphthalene ring residual group is a 1,5-—, 1,6-—, or 2,6-—substituent. The polynuclear epoxy acrylate compound (b) represented by the general formula (2a) or (2b) may be an unsaturated monobasic acid (c) containing the polynuclear epoxy compound represented by the following general formula (1 0). It is obtained by reacting in the presence or absence of the aforementioned organic solvent in the coexistence of a polymerization inhibitor and a reaction catalyst. 0Z1

Factory I CH2 —CH—CHz — 0—X—〇--CH2 —CH-CH2 —ο- γ-ο—

\ / L 〇OZ1 -ch2 -ch-ch2 -0-xo——ch2 -ch-ch2 A hydrogen atom or a group represented by the general formula (4). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to verify the polynuclear compound shown in the above general formula (10), the unsaturated polynuclear epoxy acrylate compound can be obtained by reacting a monocarboxylic acid (c) containing a + saturated I group ( .b), the polynuclear epoxy compound 'shown in the general formula (10) above is compounded to contain an epoxy group in the compound, in which the molar ratio of the epoxy group is 0.8 to 1.3 moles and the unsaturated group is contained. The monocarboxylic acid is heated in an inert solvent or without a solvent at about 60 to 150 ° C, preferably 70 to 130 ° C, and preferably in the presence of air. In order to prevent gelation due to polymerization during the reaction, hydroquinones such as methylhydroquinone, hydroquinone and the like are used; the Chinese national standard (CNS) A4 specification (210X297 mm) is applied to this paper size -26-524813 A7 _____B7 5 2. Description of the invention (24) (Please read the notes on the back before filling this page) Known commonly used polymerization inhibitors such as benzoquinone, benzoquinone, etc. To shorten the reaction time, it is better to use an esterification catalyst. Esterification catalysts can be used, for example, tertiary amines such as N, N-dimethylaniline, pyridine, triethylamine and their hydrochloride or bromate; tetramethylammonium chloride, triethylbenzyl chloride Quaternary ammonium salts such as bases; sulfonic acids such as p-toluenesulfonic acid; sulfonium salts such as dimethyl arsenate and methyl sulfamate; imidazole compounds such as 2-ethyl-4-methylimidazole; triphenylphosphine, Phosphines such as tri-n-butylphosphine; metal halides such as lithium chloride, lithium bromide, stannous chloride, zinc chloride and the like are known and commonly used. Inert solvents are available, for example, toluene, xylene and the like. Representatives of the above-mentioned unsaturated monocarboxylic acids (c) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs include acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate Ester, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenyl (meth) acrylate Unsaturated diol anhydride adducts of hydroxyl-containing acrylates such as propylene oxide, caprolactone (meth) acrylate, and the like. Particularly preferred are acrylic acid and methacrylic acid. These unsaturated monocarboxylic acids may be used alone or in combination of two or more. The number average molecular weight of the polynuclear epoxy acrylate compound (b) of the present invention is 400 to 10,000, preferably 500 to 7,000 ', and more preferably 500 to 5,000. When the number-average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is insufficient. On the other hand, if it exceeds 10, 000, the solubility in the solvent decreases, which is not good. The multi-core epoxy acrylate compound of the present invention can be used alone or in combination with other paper sizes of the Chinese National Standard (CNS) A4 (210X297 mm) -27-524813 A7 B7 V. Description of the invention (25) Epoxy resin Like ordinary epoxy compounds, a hardener can be added to harden it if necessary. (Please read the precautions on the back before filling out this page) Epoxy resins can be used individually or in combination of two or more of the conventionally known epoxy resins (D) illustrated below. As the hardening agent and the hardening accelerator, various conventionally known compounds exemplified previously can be used. In addition, the multi-core epoxy acrylate compound of the present invention can be used alone or in combination with other photosensitive (meth) acrylate compounds. When the photosensitive (meth) acrylate is used in common, a photopolymerization initiator is added. Hardened by irradiation with active energy rays. For other photosensitive (meth) acrylate compounds and photopolymerization initiators, various conventionally known photosensitive (meth) acrylate compounds (B) and photopolymerization initiators (C) can be used as exemplified below. Furthermore, the above-mentioned multi-core epoxy acrylate compound can be used alone or in combination with other photosensitive (meth) acrylate compounds. The organic peroxide or azo compound can be used for thermal polymerization, organic peroxide, and accelerator. It is hardened by normal temperature polymerization. Organic peroxides printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs include tertiary butyl perbenzoate, tertiary butyl per 2-ethylhexanoate, benzamidine peroxide, and cyclohexanone peroxide , Methyl ethyl ketone peroxide, bis-4-tertiary-butylcyclohexyl peroxydicarbonate, etc. These can be used alone or in combination of two or more. The azo compound may be a known compound such as azobisisobutyronitrile alone or in combination of two or more. As the accelerator, known salts of polyvalent metals such as octanoic acid and naphthenic acid such as cobalt, iron, and manganese, organic amines such as dimethylaniline, diethylaniline, p-toluidine, and ethanolamine can be used. Use alone or in combination of two or more. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -28 524813 A7 B7 V. Description of the invention (26) (Please read the precautions on the back before filling this page) So, the multi-core epoxy of the present invention An epoxy acrylate resin composition composed of an acrylate compound, a photopolymerization initiator, a hardener, or even a hardening accelerator when necessary, can be easily prepared by the same method as the conventional method. A hardened composition. For example, the polynuclear epoxy acrylate compound, hardener, filler, and other additives of the present invention are thoroughly and uniformly mixed with an extruder, a kneader, a roller, etc. as necessary to obtain an epoxy acrylate resin composition. After the composition is melted, it is formed by injection molding or transfer molding machine, and then heated at 20 to 200 ° C to obtain a hardened product. In addition, the epoxy acrylate resin composition is dissolved, and it is impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other substrates, and dried by heating to obtain a film, which is formed by hot pressing or The hardened material can also be obtained by irradiation with active energy rays. The epoxy acrylate resin composition may be mixed with various additives such as inorganic or organic fillers, if necessary. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the multi-core epoxy acrylate compound, photopolymerization initiator, hardener, and even hardening accelerator when necessary It is soluble in solvents and adjusted to a viscosity suitable for the coating method. According to the research of the inventors, it is found that, as described above, the linear epoxy compound containing a regular repeating aromatic ring is a copolymerization of a biphenyl skeleton and a naphthalene skeleton with a high softening point, or a bisphenol skeleton and a naphthalene skeleton. The alcoholic hydroxyl group of the side chain in the linear epoxy compound is an epoxy compound obtained by reacting with an epoxy halopropane in the presence of a solvent, reacting with an unsaturated monocarboxylic acid, and using a polybasic acid anhydride with the obtained epoxy Alkali-soluble active paper obtained from the reaction of acrylate compounds The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -29 · 524813 Α7 Β7 V. Description of the invention (27) Performance line hardening resin, high temperature resistance A resin composition having toughness and containing such an active ingredient can lead to a hardened product having excellent plating properties, electrical properties, flexibility, and absorption properties. That is, the activity of the present invention can be described as a monocarboxylic acid of the polynuclear ring group represented by the general formula (5). C c), and b ') is the opposite of polybasic acid anhydride (d), and is a compound containing regular repetition Because of the linear structure, it can obtain the adhesion to the substrate, non-electrolytic hygroscopicity and PC resistance (excellent thermal stability under pressure cooker, balanced heat-resistant energy ray-curable resin is light-curable heat resistance) , Adhesiveness, resistance to electroless electrowetting, and resistance to P c T (pressure cooker test line hardening resin (A), the oxygen compound (a ') contains unsaturated unsaturated epoxy acrylate compound (should, Aromatic rings with different light-hardening and alkali-developing properties can be used to obtain hardened products with high mechanical strength and high heat resistance. At the same time, excellent hardened products such as electroplating, electrical properties, flexibility, and test resistance can be obtained. (Please read the notes on the back before filling this page)

0M CH2 —CH—CH2 —0—X, -10 • CH2 —CH—CH2 —0—Ύ * ’one 〇— 〇

0M Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, a CH2 —CH—CH2 —0—X '10— -CH2 —CH—CH2 \ / 0 (5) where X' and Y 'tables are different from each other Divalent aromatic ring, M represents an epoxy propyl group, methyl glycidyl group and / or a hydrogen atom, η is an integer from Table 1 to the following. The active energy ray hardenability of the present invention is described in detail. The resin, and light hardening using the same Each component of the thermosetting composition. First of all, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -30-524813 A7 _B7 V. Description of the invention (28) The active energy ray hardening resin of the invention. (Please read the precautions on the back before filling this page) The polynuclear epoxy compound (3,) shown by the general formula (5) above is based on difunctional aromatic epoxy compounds and difunctional aromatic alcohols, such as As mentioned above, a known esterification catalyst is used for cross-polymerization in a solvent or without a solvent. In a known aprotic polar solvent such as formamidine, N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene, in the presence of an alkali metal hydroxide such as sodium hydroxide Derived from the reaction. In the synthesis of the above-mentioned active energy ray-curable resin, the bifunctional aromatic epoxy compound and the difunctional aromatic alcohol are not limited to those previously exemplified, but of course, the bifunctional aromatic epoxy compounds and Difunctional aromatic alcohols are preferred. Secondly, the polynuclear epoxy compound (a ') represented by the above general formula (5) is a monoresidue containing unsaturated group, as described above, in the presence of the organic solvent of the Intellectual Property Bureau employee consumer cooperative printed by the Ministry of Economic Affairs In the absence or presence, polymerization inhibitors such as hydroquinone, oxygen, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, 2-ethyl-4-methyl In the coexistence of reaction catalysts such as imidazole compounds such as imidazole and phosphorus compounds such as triphenylphosphine, the 'multinuclear epoxy acrylate compound (b') is usually reacted at about 80 to 130 ° C. According to the alcoholic hydroxyl group of the epoxy acrylate compound (b ') formed by the above reaction, the active energy ray-curable resin (A) of the present invention can be obtained by reacting it with the polybasic acid anhydride (d). In this reaction, the polybasic acid anhydride The amount of (d) is suitable for the alcoholic hydroxyl group and the anhydride group in the above reaction product at a ratio of 9 9: 1 to 1... 9, and the range of the acid hydrazone is preferably 50. 0 to 200 mg / KOH / g, preferably 50 to 120 mg KOH / g. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -31-524813 A 7 B7 V. Description of the invention (29) (Please read the precautions on the back before filling this page) Active energy ray hardening resin When the acid sulfonium (A) is less than 50 mg KOH / g, the solubility of the alkaline aqueous solution is poor, and the formed coating film is difficult to develop. On the other hand, if it is higher than 200 mg KOH / g, the surface of the exposed portion will not develop well regardless of the exposure conditions. The reaction is carried out in the presence or absence of the aforementioned organic solvent in the presence of polymerization inhibitors such as hydroquinone and oxygen, usually at about 50 to 130 ° C. In this case, if necessary, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl chloride, imidazole compounds such as 2-ethyl-4 monomethylimidazole, and triphenylphosphine may be added. And other phosphorus compounds as catalysts. The above-mentioned polybasic acid anhydrides are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Examples include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, norbornene dianhydride, 3,6 —bridged Tetrahydrophthalic anhydride, methyl bridged tetrahydrophthalic anhydride, tetrabromophthalic anhydride and other alicyclic dibasic anhydrides; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentaenyl succinic anhydride, phthalic anhydride , Trimellitic anhydride, aliphatic or aromatic dibasic anhydride, or biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic acid Aliphatic or aromatic quaternary acid dianhydrides such as acid anhydride, benzophenone tetracarboxylic dianhydride, etc., These can be used singly or in combination of two or more. Among them, alicyclic diacid anhydride is particularly preferable. The number-average molecular weight of the active energy ray-curable resin (A) of the present invention is 400 to 10,000, more preferably 500 to 7,000, and more preferably 500 to 3,000. When the number-average molecular weight of the active energy ray-curable resin is less than 400, the toughness of the obtained hardened product is insufficient. On the other hand, if it exceeds 10, 000, the solubility in the solvent decreases, which is not good. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -32-524813 A7 B7 V. Description of the invention (30) (Please read the precautions on the back before filling this page) The alkali of this invention can develop light The curable and thermosetting resin composition may contain, in addition to the above-mentioned active energy ray-curable resin (A), one or more (methyl) groups of one of the molecules of the photosensitive (meth) acrylate compound (B). ) Acrylic fluorenyloxy, a photosensitive (meth) acrylate compound that is liquid, solid, or semi-solid at room temperature. These photosensitive (meth) acrylate compounds are used for the purpose of improving the photoreactivity of the composition. The photosensitive (meth) acrylate compound is a liquid at room temperature. In addition to improving the photoreactivity of the composition, it can also help adjust the composition to a viscosity suitable for various coating methods and dissolve in an alkaline aqueous solution. Sexual effect. However, if a large amount of a photosensitive (meth) acrylate compound that is liquid at room temperature is used, the touch dryness of the formed coating film cannot be obtained, and the characteristics of the coating film tend to deteriorate. Not good. The blending amount of the photosensitive (meth) acrylate compound (B) is 10 to 60 parts by mass based on 100 parts by mass of the active energy ray-curable resin (A) (in terms of solid content, the same below), and 15 to 50 parts by mass is preferred. The above-mentioned photosensitive (meth) acrylate compounds are printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. Hydroxyl-containing acrylates; water-soluble acrylates such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc .; trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. Polyfunctional polyester acrylates of polyfunctional alcohols; polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A, or ethylene oxide adducts of polyfunctional phenols such as bisphenol A and biphenol. Acrylates of finished products; the isocyanates of the above-mentioned hydroxyl-containing acrylates are applicable to Chinese paper standard (CNS) A4 · (210X297 public envy) -33-" 524813 A7 B7 V. Description of the invention (31) ( (Please read the precautions on the back before filling this page) Modified polyfunctional or monofunctional polyurethane acrylate; bisphenol A diglycidyl ether, hydrogenated bis-A dipropylene oxide Qing or phenolic type epoxy paint (meth) acrylate, epoxy acrylate adduct, and said the acrylate of methacrylate and the like corresponding to these may be used alone or in combination of two or more kinds. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloxy groups in one molecule is preferred. The photopolymerization initiator (C) can be exemplified by benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin ethyl ethers; acetamidine Benzene, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Category; 2-methyl-1— [4-mono (methylthio) phenyl] _2-morpholinaminoacetone-1, 2-benzyl-2-dimethylamino group Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Printing 1- (4-morpholinophenyl) -1 monomethyl ethyl ketone, N, N-dimethylamino ethyl acetophenone and other amino ethyl acetophenones; 2-methyl anthraquinone, 2- ethyl Anthraquinones, 2-tert-butylanthraquinone, 1-anthraquinone chloride, and other anthraquinones; 2,4-dimethylthioanthone, 2,4-diethylthioanthone, 2-chlorosulfan Anthrone, 2,4-diisopropylthioxanthone and other thioanthones; acetone ketal, benzyl dimethyl ketal and other ketals; benzyl peroxide, isopropyl Organic peroxides such as benzene peroxide; 2,4,5-triarylimidazole dimer, tetra Thiol compounds such as alcohol riboflavin, 2-fluorenyl benzimidazole, 2-sulfobenzimidazole, 2-fluorenylbenzothiazole, etc .; 2, 4, 6—reference 1S—trioxine, 2, Organic halides such as 2,2-tribromoethanol, tribromomethylphenyl, etc .; benzophenones, benzophenones such as benzophenone, 4,4'-bisdiethylaminobenzophenone or oxanthracene Ketones; 2,4,6-trimethylbenzene This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) -34-524813 A7 __ B7 V. Description of the invention (32) Phenylphosphine oxidation Things. (Please read the precautions on the back before filling this page) These known commonly used photopolymerization initiators can be used alone or in combination of two or more. N, N-dimethylaminobenzoic acid ethyl ester, Light-starting auxiliaries such as tertiary amines such as N'N-dimethylaminoisobenzoate, pentyl-4, dimethylaminobenzoate, triethylamine, triethanolamine, etc. Titanocene compounds, such as CG I — 7 8 4 (Cibaite Chemical Co., Ltd.) that absorb in the visible range can be added to promote photoreaction. A particularly good initiator for photopolymerization is 2-methyl-1 1- [4-mono (methylthio) phenyl] -2 2-morpholinaminoacetone-1, 2-benzyl-1 2-dimethyl. Amino-1,1- (4-morpholinylphenyl) butan-1, one-ketone, etc., but not specific to them, as long as there is absorption in the ultraviolet or visible light range, and unsaturated groups such as (meth) acrylfluorenyl are used as The radical polymerizer is not limited to a photopolymerization initiator and a photoinitiator, and can be used alone or in a large amount. The amount of the photopolymerization initiator (the total amount when the photoinitiator is used) is preferably 0.1 to 25 parts by mass to 100 parts by mass of the active energy ray-curable resin (A), Printed with 0.5 to 20 parts by mass as a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the blending amount of the photopolymerization initiator is less than the above range, the irradiation with active energy rays cannot be hardened, or the irradiation time must be extended, and it is difficult to obtain proper coating film properties. On the other hand, the addition amount of the photopolymerization initiator is more than the above range, and the photohardenability does not change, which is not economically good. The photocurable and thermosetting composition of the present invention is to dissolve the active energy ray-curable resin (A) and the photosensitive (meth) acrylate compound (B), and adjust the composition to be suitable The viscosity of the coating method can be formulated with the organic solvents previously exemplified alone or in combination of two or more. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 cm) -35-524813 A7 B7 V. Description of the invention (33) · (Please read the notes on the back before filling this page) The above-mentioned multifunctional epoxy compound (D). Specific examples are Epicote 8 2 8, Epicote 8 3 4, EPic. te 10 0 1, Epicote 1 0〇4 'Epicolon 8 4 0, Epicolon 8 5 0, ^ Piclon 1 0 5 0, Epiclon 2 0 5 5' ) Epotote YD — 011, YD — 013, YD — 1 27, YD — 1 28, D · E · R · 317, DER331, DER661, D • E · r · 6 6 4. Araldite 6 〇7 manufactured by Cibaite Chemicals Company 1, Araldite 6 0 8 4, Araldite GY 250, Araldite YG 2 60, Sumi EP〇xy ESA—011, ESA— manufactured by Sumitomo Chemical Industry Co., Ltd. 014, ELA— 1 1 5. ELA— 1 28 'A.E.R.330, A.E.R. 3 3 1 > Asahi Kasei Industrial Co., Ltd. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 61, AER664, etc. (all are trade names) Bisphenol A epoxy resin; Epicote YL 9 0 3 made by Japan Epoxy Resin Co., Ltd. Epotote YDB-400, YDB — 500 made by (stock), D. E.R. 542 made by Dow Chemical Company, Araldite 8 0 1 1 made by Cibaite Chemicals, and Sumitomo Chemical Industry (stock) made Sumi Epoxy ESB — 400, E SB-700, A. E · R · 7 1 1, A · E · R · 7 1 4 and other (all trade names) brominated epoxy resins manufactured by Asahi Kasei Corporation Epicote made by Japan Epoxy Resin Co., Ltd. This paper size is applicable to Chinese National Standard (CNS) A4 specifications {210X297 mm) -36-524813 A7 B7_ V. Description of the invention (34) (Please read the precautions on the back before (Fill in this page)

15 2. · Epicote 154 'DEN by Dow Chemical Company • 43 1. D · E · N · 438' Epiclon N — 7 3 0, Epiclon N — 7 7 0 Epiclon N—865, EP〇tote ya [) 〇1 ^ —70 1, Dong 〇00] ^ — 7 04, Araldite ECN 1 2 3 5 by Cibate Chemical Co., Ltd. Araldite ECN 12 7 3. Araldite ECN 1 2 9 9. Araldite XPY 307, EPPN-201, E-CN-1025, E-CN-1020, .E-CN-104 , RE — 3 06; Sumi Epoxy eSCN-195X, ESCN-2 20 'manufactured by Sumitomo Chemical Industries (stock) Printed by ARECEN of Asahi Kasei Corporation (235), ECN — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 9 9 and other (both trade names) lacquer-type epoxy resins; Epicolon 8 3 0 manufactured by Dainippon Ink Chemical Industry Co., Ltd .; Epicote 8 0 7 manufactured by Japan Epoxy Resins (stock); Stock) made by Epitote YDF-170, YDF-175, YDF-2004 »Araldite XPY306 made by Cibaite Chemicals Co., Ltd. (all are Trade name) of bisphenol F-type epoxy resin; Hydrogenated bisphenol A type of epoxy resin such as Epocote ST-2004, ST-2007, ST-3 0 0 0 (trade name) manufactured by Toto Kasei Co., Ltd .; Japan Epicote 6 0 4 'made by epoxy resin (stock)' Epotote made by Toto Kasei (stock) γ Η — 4 3 4, manufactured by Cibato Chemical Co., Ltd.

Araldite MY720, S Umi Epoxy E LM made by Sumitomo Chemical Industry Co., Ltd. — 1 2 0, etc. (both trade names) Epoxy amine type ring This paper is sized to Chinese National Standard (CNS) A4 (210X297 mm) -37-524813 V. Description of the invention (35) Oxygen resin; Araldite CY-3 50 (trade name) and other Hein-type epoxy resins made by Cibaite Chemicals; CeloxWe made by Daicel Chemical Industry Co., Ltd. 2 0 2 1, manufactured by Cibaite Chemical Company

Araldite CY175, CY179, etc. (both trade names) are alicyclic epoxy resins; YL — 9 3 3 made by Japan Epoxy Resin (stock), Τ · Ε · Ν · made by Dow Chemical Company, EPPN — 501 , EP PN — 502, etc. (both trade names) trihydroxyphenyl methyl formaldehyde epoxy resin; YL — 6056, YX — 4000, YL — 6 121 (both are made by Japan Epoxy Resins) (Brand name) and other cresol-type or biphenol-type epoxy resins, or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku), EPX ~ 3 manufactured by Asahi Kasei Kogyo Kogyo Co., Ltd., printed by employees of the Intellectual Property Bureau, Ministry of Economy (Please read the precautions on the back before filling in this page, > 0, EXA-1514 (trade name) made by Dainippon Ink Chemical Industry Co., Ltd.) and other bisphenol S epoxy resins; Japanese epoxy resins · Epicote 1 5 7 S (trade name) and other bisphenol A type lacquer-type epoxy resins; Epkote YL-9 3 1 made by Japan Epoxy Resins (stocks), made by Cibaite Chemicals Co., Ltd. Araldhe 1 6 3 etc. (both trade names) tetrahydroxyphenylethane type epoxy resin; Cibat Chemical Co., Ltd. Araldite PT810, TE PIC, etc. (both trade names) made by Nissan Chemical Industries, Ltd. (both trade names) heterocyclic epoxy resins; Diepoxypropylphthalate resins, such as Blenmer-DGT, made by Ben Fats & Oils Co., Ltd. ; Tetsu epoxy xylenol ethane resins such as ZX-1 0 6 3 manufactured by Toto Kasei Co., Ltd .; ESN-1 90, ESN 3 6 0 manufactured by Nippon Steel Chemical Co., Ltd., Dainippon Ink Chemical industry (stock) system Η P.-4 0 3 2, ΕΑΑ-4750, ΕΑΑ-4700 and other naphthalene-based ring paper sizes apply Chinese National Standard (CNS) A4 specifications (210X297 mm) -38 524813 A7 B7_ V. Description of the invention (36) (Please read the precautions on the back before filling in this page) Oxygen resin, HP-7 2 0 0, HP — 7 2 0 0H, etc. made by Dainippon Ink Chemical Industry Co., Ltd. Cyclopentadiene-based epoxy resins; epoxy methacrylate copolymer epoxy resins such as CP — 50S, CP — 50M made by Japan Oils & Fats Co., Ltd .; even cyclohexylmaleimide and cyclic Copolymer epoxy resin of oxypropyl methacrylate, etc., but is not limited to these. These epoxy resins may be It can be used alone or in combination of two or more. Among them, biphenol type or bixylenol type epoxy resin, or a mixture thereof is preferred. When other epoxy resins are used, the above active energy ray-curable resin in the composition is also used. (A) 100 parts by mass, preferably a proportion of 5 parts by mass or more. The multifunctional epoxy resin (D) as described above can improve the adhesiveness and heat resistance of the solder resist due to heat curing. The blending amount is preferably 100 parts by mass or more and 100 parts by mass or less, and preferably 25 to 60 parts by mass, with respect to the above-mentioned active energy line curable resin (A). When the blending amount of the polyfunctional epoxy compound (D) is less than 10% by mass, the cured film has a high hygroscopicity, and the PCT resistance is liable to decrease, and the heat resistance of the solder and the electroless plating resistance are liable to decrease. On the other hand, if it exceeds 100 parts by mass, the developability of the coating film and the electroless plating resistance of the cured film are deteriorated, and the P C T resistance is also deteriorated. For example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-benzene, etc. are printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Imidazole derivatives such as imidazole, 4-phenylimidazole, 1-cyanamide ethyl-2-phenylimidazole, 1- (2-cyanaminoethyl) -2-ethyl-4-methylimidazole: bis Cyanamide, benzyl dimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl China National Standard (CNS) A4 Specification (210X297 mm) -39-524813 Α7 Β7 V. Invention Description (37) (Please read the notes on the back before filling this page) Base amine, '4 monomethyl-N, Amine compounds such as N-dimethylbenzylamine, hydrazine compounds such as hydrazine adipate and hydrazine sebacate; phosphides such as triphenylphosphine and the like; 2) ^ 12 — A, 2MZ-0K, 2PHZ, 2P4BHZ, 2 P 4 Μ Η Z (all are trade names of imidazole compounds), U — CAT3503X, U — CAT made by Sunapro 3502X (both trade names of dimethylamine barrier isocyanate compounds), D B U, DBN, U-CATSA10 2, U — CAT5002 (both bicyclic fluorene compounds and their salts), etc. It is not limited to this, as long as it is an epoxy resin, a catalyst, or a catalyst that promotes the reaction between an epoxy group and a carboxyl group, it is preferably used alone or in combination. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropionyloxyethyl-S-three farming, guanidamine, acetoguanamine, melamine, adhesion-improving functions can also be used, 2-vinyl-1,2,4-diamino-S—three-coated, 2-vinyl-4,6—di-amino-printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees ’Cooperatives, printed base-S—three-coated, trimeric isocyanate Adducts, 2,4-diamino-6-methacrylic acid, ethoxyethyl-S-trioxine, trimeric isocyanate adducts, etc., S-three cultivated derivatives are preferred These adhesion-imparting compounds and the above-mentioned curing catalyst. The blending amount of the hardening catalyst may be a normal proportion, for example, 100 parts by weight of the active energy ray-curable resin (A), 0. 1 to 20 parts by mass, and 0. 5 to 1 5 · 0 parts by mass is preferred. In the photocurable and thermosetting resin composition of the present invention, barium sulfate, barium titanate, silicon oxide powder, fine powdered silicon oxide, amorphous silicon oxide, crystalline silicon oxide, fused oxide sand, Spherical silicon oxide, talc This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -40 _ 524813 A7 __B7 V. Description of the invention (38) (Please read the precautions on the back before filling this page), Clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, mica and other known inorganic fillers are commonly used alone or in combination of two or more. The purpose of use is to suppress the hardening and shrinkage of these coating films, and improve the properties such as adhesion and hardness. The blending amount of the inorganic constant filling tincture is 10 to 300 parts by mass per 100 parts by mass of the active energy ray-curable resin (A), and preferably 30 to 200 parts by mass. The composition of the present invention can be further blended with phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and other commonly used colorants, hydroquinone, hydrogen, etc. if necessary. Known and commonly used thermal polymerization inhibitors such as quinone monomethyl ether, tertiary butyl catechin, catechol, pyrogallol, phenothiazine, micronized silica, organic bentonite and other known commonly used thickeners, silicones, Defoamers and / or leveling agents such as fluorine-based polymers and / or leveling agents, silane coupling agents such as imidazole-based, thiazole-based, and triazole-based additives are commonly known. The photo-curable / thermo-curable resin composition of the present invention, which is composed of the above-mentioned composition by the Consumers' Cooperative of the Ministry of Economic Affairs and the Ministry of Economic Affairs, can be diluted as necessary to adjust the viscosity suitable for the coating method. The screen printing method, curtain coating method, spray coating method, roll coating method, etc. of the printed circuit board forming the circuit are applied, and the organic solvent contained in the composition is evaporated to dryness at a temperature of about 60 to 100 ° C to form No cracking coating. Thereafter, the selective exposure of the active energy rays through a mask formed with the pattern is used to develop the resist pattern by developing the unexposed portion with a dilute aqueous alkali solution. Active energy ray irradiation 'or final hardening (formal hardening) only after heating and hardening to form heat resistance, adhesion, electroless plating resistance, electrical properties, flexibility, moisture absorption resistance, and PCT resistance (pressure cooker test) ) Hardened film with excellent properties (The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-41-524813 A7 B7 V. Description of the invention (39) Resist film)) (Please read the first Please fill in this page for the matters needing attention) The above alkaline aqueous solution can be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and other alkaline aqueous solutions. In addition, for the light source for light hardening, suitable ones include a low-pressure mercury lamp, a medium-pressure mercury lamp, a local-pressure mercury lamp, an ultra-local-pressure mercury lamp, a gas lamp, or a metal halide lamp. In addition, laser light or the like may be used as the active energy ray. Hereinafter, the present invention will be specifically described using examples and comparative examples. However, the following examples are only for the purpose of illustrating the present invention and are not intended to limit the present invention. In addition, the following "parts" and "%" are based on quality unless otherwise specified. Synthesis Example 1 In a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, 169 parts of 1,5-dihydroxynaphthalene, and epoxy equivalent 194 g / equivalent 3'3 ', 5, 5 130 parts of 5′-tetramethyl-1, 4 ′ 12 printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 1,130 parts of hydroxybiphenyl dipropylene oxide, and dissolved in 120 t under stirring in nitrogen. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 t, while the temperature was maintained at 150 ° C. The surface reaction was performed for about 90 minutes to obtain an epoxy equivalent of 4.02 g / Equivalent epoxy compound. Next, the temperature in the flask was cooled to below 70 ° C, and 192 parts of epichlorohydrin and 169 parts of dimethylene were added. The temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed in 90 minutes, and 114 parts of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction, the excess of epoxy, chloropropane and dimethylacetone were distilled under reduced pressure at 120 ° C and 50mm column to dissolve the reaction products containing parasalt and dimethylacetate in The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 42-524813 A7 B7 V. Description of the invention (40) (Please read the precautions on the back before filling this page) Isobutyl A . Thereafter, methyl isobutyl ketone was recovered from the oil layer by evaporation, and an epoxy equivalent of 3.0 g / equivalent polynuclear epoxy compound (a to 1) was obtained. The obtained polynuclear epoxy compound (a-1) is epoxidized in the alcoholic hydroxyl groups 1.76 in the general formula (7a) described above when calculated from the epoxy equivalent s. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 45 ° (). Example 2-In a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, add 232 parts of 1,5-dihydroxynaphthalene, and epoxy 194 g / equivalent 3'3,3,5,5'-tetramethyl-1,4,4'-dioxetylbiphenylenedioxypropyl ether 7 parts, 1 2 under stirring under nitrogen. t: dissolved. After that, 0.65 parts of triphenylphosphine was added, and the temperature printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in the flask was raised to 150 t, while the temperature was kept at 150 t. The reaction took about 90 minutes. An epoxy equivalent of 5 4 4 g / equivalent epoxy compound (2) was obtained. Next, the temperature in the flask was cooled to below 70 ° C, 1 8 3 9 parts of epichlorohydrin was added, and dimethylene was ground 16 Ninety parts, heated to 70 ° C with stirring and maintained. After that, disperse in 90 minutes and add 159 parts of 96% sodium hydroxide. After the addition, react for 3 hours. After the reaction is completed, the excess ring Most of the oxychloropropane and dimethylarsox were distilled under reduced pressure at 120 ° C, 50 mm, and the reaction product containing parasalt and dimethylarsox was dissolved in methyl isobutyl ketone for washing. Thereafter, The methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 376 g / equivalent polynuclear epoxy compound (a-2). The obtained polynuclear epoxy compound (a-2) was obtained from the epoxy equivalent of this paper Applicable to China National Standard (CNS) A4 specification (210X297 mm) -43-524813 A7 B7 V. Description of invention (41) Calculation, Then about 1 · 0 5 of the alcoholic hydroxyl groups in the general formula (7 a) above are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl groups is 4 (please read the precautions on the back before filling in (This page)

6%. The infrared absorption spectrum (determined by Fourier transform infrared spectrophotometer FT-IR) and nuclear magnetic resonance spectrum (solvent CDC 1 3, reference substance TMS (tetramethylsilane) of the polynuclear epoxy compound (a-2) obtained in this synthesis example. )) Each is shown in Figures 1 and 2. Synthesis Example 3 In a flask equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, 274 parts of 1,5-dihydroxynaphthalene 'and 194 g / equivalent of epoxy resin were added to 3,3', 5,5'- 10 2 5 parts of tetramethyl-1,4'-dihydroxydiphenyl dipropylene oxide were dissolved in .120 ° C under stirring under nitrogen. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C, while maintaining the temperature at 150 ° C for about 90 minutes, and an epoxy equivalent of 7 2 3 g was obtained. / Equivalent epoxy compound (3). Next, cool the temperature in the flask to below 70 ° C, add 179 parts of epichlorohydrin, and 190 parts of dimethylamine, and heat up to the printing of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs with stirring. 70 ° C and hold. Thereafter, it was dispersed in 90 minutes, and 92% of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction, the excess of epichlorohydrin and dimethyl arsenate were distilled under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction product containing para-salt and dimethyl arylene in formazan. Isobutyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 4.8 g / equivalent polynuclear epoxy compound (a-3). The obtained multi-core epoxy compound (a-3), if the Chinese equivalent standard (CNS) A4 specification (210 × 297 mm) is applied from the epoxy equivalent of the paper size, -44-" ~ 524813 A7 B7 V. Description of the invention (42) calculation Then, about 1.3 2 of the alcoholic hydroxyl groups 2.93 in the general formula (7a) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 4 5 (Please read the precautions on the back before filling this page)%. Synthesis Example 4 In a flask equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, 169 parts of 2,6-dihydroxynaphthalene, and epoxy equivalent 194 g / equivalent of 3, 3 ', 5, 5', and 14 were added. Methyl-4,4'12 Printed 1,130 parts of hydroxydiphenyl dipropylene oxide by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, dissolved in nitrogen at 120 t under stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C, while maintaining the temperature at 150 ° C:-The side reaction was performed for about 90 minutes, and epoxy equivalent of 37.1 g was obtained. / Equivalent epoxy compound (4). Next, the temperature in the flask was cooled to below 70 ° C, and 195 parts of epichlorohydrin and 169 parts of dimethyl arylene were added, and the temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed in 90 minutes, and 23% of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction was completed, the excess epichlorohydrin and the majority of Ershen Yashuo were evaporated under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction products containing parasalt and dimethyl Yasuo in methyl isobutyl formamide Ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain a polynuclear epoxy compound (a-4) having an epoxy equivalent of 267 g / equivalent. If the obtained polynuclear epoxy compound (a-4) is calculated from the epoxy equivalent, there are 0 ·· 9 9 epoxidation of the alcoholic hydroxyl groups 1. 6 of the general formula (7 a). Therefore, the epoxidation rate of alcoholic radicals is 60%. ○ This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm 1 -45 · 524813 A7 B7. V. Description of the invention (43) Synthesis example 5. (Please read the precautions on the back before filling in this page) Except that the use amount of 96% sodium hydroxide is 58 parts, the epoxy equivalent of 3.09 g / equivalent polynuclear epoxy compound (a — 5). If the obtained polynuclear epoxy compound (a-5) is calculated from the epoxy equivalent, then 0.5 to 50 of the alcoholic hydroxyl groups 1.65 in the general formula (7a) described above are epoxidized. The epoxidation rate of alcoholic hydroxyl groups is 30% Synthesis Example 6 * In a reaction vessel equipped with a gas introduction pipe, a stirring device, a cooling pipe and a thermometer, '80 equivalents of hydroxyl groups / equivalent of 1, 5-dihydroxynaphthalene are wisdom 2 2 4 · 2 copies printed by the employees' cooperative of the property bureau, and 189 g / equivalent bis-acid A type epoxy compound (trade name "Epicote 828") made by Japan Epoxy Resin (stock) 1075. 8 parts, dissolved under stirring at 1 10 ° C. After that, triphenylphosphine 0.65 parts was added The temperature in the reaction vessel was raised to 150 ° C, and the temperature was kept at 150 ° C while the reaction was carried out for about 90 minutes to obtain an epoxy equivalent of 452 g / equivalent epoxy compound (6). The temperature in the reaction vessel was cooled to 40 ° C, 192 parts of epichlorohydrin was added, and 169 parts of toluene were dissolved. Then 70 parts of tetramethylammonium bromide was added, and the temperature was raised to 60 ° C with stirring. After that, 364 parts of 48% sodium hydroxide aqueous solution was continuously added dropwise over 60 minutes. After the dropwise addition, the reaction was continued for 6 hours. After the reaction was completed, excess unreacted epichlorohydrin and most of toluene were added. Recovered under reduced pressure, the reaction products containing by-product salt and toluene will be used. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -46-524813 A7 B7 V. Description of the invention (44) (Please read the back first Note: Please fill in this page again) Dissolve in methyl isobutyl ketone for washing. After separating the organic solvent layer and water layer, distill off the methyl isobutyl ketone from the organic solvent layer under reduced pressure to obtain epoxy equivalent 2 7 7 g / equivalent polynuclear epoxy compound (a-6). The obtained polynuclear epoxy compound (a-6) ) 'If calculated from the epoxy equivalent, about 1.59 of the alcoholic hydroxyl groups of 1.98 in the epoxy compound (6) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl groups is about 80%. Synthesis Example 7 In a reaction vessel equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, hydroxy equivalent 80 g / equivalent 1,25-dihydroxynaphthalene 219.2 parts, and Japanese epoxy resin (stock) were added. An epoxy equivalent of 19 2 g / equivalent xylenol type epoxy compound (trade name "Epicote YX4000") was made into 1080 · 8 parts, and the sample was dissolved at 1 10 t under nitrogen stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the reaction vessel was raised to 150 ° C, while maintaining the temperature at 150 ° C:-The reaction was carried out for about 90 minutes to obtain an epoxy equivalent of 4 5 1 G / equivalent of epoxy compound (7). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs followed by cooling the temperature in the reaction vessel to 40 ° C, adding 189 parts of epichlorohydrin, and 169 parts of toluene dissolved, and then adding tetramethyl bromide 6-9 parts of ammonium were heated to 60 t with stirring and kept. Thereafter, 360 parts of a 48% sodium hydroxide aqueous solution was continuously added dropwise over 60 minutes. After dropping, 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 by-product salt and methylbenzene was dissolved in methyl isobutyl ketone for washing. Separate the organic solvent layer and water layer into paper. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -47-524813 A7 _____ B7 V. Description of the invention (45) After separation, remove the organic solvent layer by vacuum distillation. Distilling out the methyl isobutyl ketone 'gives an epoxy equivalent of 278 g / equivalent polynuclear epoxy compound (a-7) ° The obtained polynuclear epoxy compound (a-7). About 1.56 of the alcoholic hydroxyl groups of 1.95 in the compound (7) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%. Examples 1 to 7 and Comparative Examples 1 to 4 Examples 1 to 7 are each a comparison of the polynuclear epoxy compounds (a-1) to (a-7) synthesized in the above Synthesis Examples 1 to 7, respectively. Examples 1 to 7 4 Each of the epoxy compounds (1) to (4) obtained in the above Synthesis Examples 1 to 4 was blended with a phenol resin (phenolic lacquer, hydroxyl equivalent of 106 g / equivalent) in the ratio shown in Table 1, Phenyl-4,5-dihydroxymethyl.imidazole (PDM I for short) and a solvent (carbitol acetate) were kneaded with a three-roller machine to obtain a thermosetting resin composition. (Please read the notes on the back before filling out this page} Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Standard State, State, China, and China I ー 4 S Ν Publication 97 2 48 524813

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7 B V. Description of the invention (46) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i Comparative example inch—H 28.6 inch S m 〇i, mi ▼ —H inch S csl o. R ··· ia \ inch gr —Ή 〇r— i 26.4 inches 〇 Example 〇- 〇 40.0 inches 〇〇 "< 40.6 inches uo MP υη ο f '' i 34.3 inches 〇 inches ο fi 39.7 inches un v〇cn Ο ι " 1 Η 23.1 Inch 〇 r—Η Csl Ο ι i 28.2 Inch g τ—Η Ο τ · Λ 34.9 Inch 〇 Composition (a_l) (a-2) (a-3) (a-4) (a-5) (a-6 ) (a-7) 〆 ^ \ / ^ N —oi cn inch > w / Phenol resin hardening accelerator (PDMI) solvent (carbitol acetate) I .----------— ( (Please read the notes on the back before filling out this page) Order Φ Flat Screen. Ding Yi-

Publication 97 2 X 49 524813 A7 B7 V. Description of the invention (47) (Please read the precautions on the back before filling out this page) Put the composition of each of the above examples and comparative examples at 80 ×: 30 minutes, then Hardened at 180 ° C for 1 hour, measured glass transition point, tensile strength, elongation, tensile elasticity, water absorption, electrical insulation, pencil hardness, and evaluated adhesion, acid resistance, and alkali resistance . The evaluation of each physical property was performed by the following method. < Glass transition temperature > The composition of each of the above Examples and Comparative Examples was screen-printed on a Teflon sheet washed and dried in advance, and dried in a hot air circulation drying oven at 80 ° C for 40 minutes. After cooling to room temperature, exposure was performed at an exposure amount of 50 mJ / cm², and it was hardened in a hot air circulation drying oven at 180 ° C for 60 minutes. After cooling to room temperature, the hardened coating film was peeled from the Teflon board to obtain an evaluation sample. The glass transition point of the sample was measured by the DM method. < Tensile strength (tensile failure strength), elongation (tensile failure elongation), and tensile modulus of elasticity > Calculated in accordance with JIS K 7172. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs < Water absorption, pencil hardness > Calculated based on Jis K 5400. < Adhesiveness > J I s D 0 2 0 2 was judged visually. The judging standards are as follows: ○ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -50- 524813 A7 _______B7_ V. Description of the invention (48) 〇: No peeling visible A: Only slight peeling X: Complete Peeler (please read the precautions on the back before filling in this page) < Electrical insulation The composition of each of the above examples and comparative examples was applied to a comb electrode B test piece of IPCB-2 5 using Pilot Seiko (stock ) The roll coater was used for full coating, and it was cured at 80 ° C for 30 minutes, and then cured at 180 ° C for 1 hour to make an evaluation substrate. A bias voltage of DC 500 volts was applied. The comb electrode was used to measure the insulation resistance 値. ≪ Acid resistance test > The substrate for evaluation of the same electrical insulation property was taken out after immersing in a 10% by volume sulfuric acid aqueous solution at 20 ° C for 30 minutes, and the state and adhesion of the coating film were comprehensively judged. The judgment criteria are as follows. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇: No visible change △: Only slight changes X: Coating film swelled or swelled off < Alkali resistance test〉 Except 10% by volume sulfuric acid aqueous solution was replaced by 10 Except for the volume% sodium hydroxide aqueous solution, it was evaluated by the same acid resistance test. The results obtained are shown in Table 2. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -51-524813 A7 B7 V. Description of invention (49) Comparative example printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs I 丨 172.4 1942.9 62.5 1_ 1 ir- ^ 〇cn CO 〇〇CO 165.1 1882.6 60.8 5.69 oo i 1 it-H < CO cn κ Csl <] 〇166.3 1907.5 61.6 5.66 〇 ^ 1 it-H 〇cn cn cn 〇〇 ... ..m, i 168.1 1936.5 3 5.64 1.05 〇K K 〇〇 Example 213.1 2340.5 70.2 5.32 r_H 〇E VO 〇〇VO 204.5 2320.3 69.4 fir-H un 0.66 〇CO K VO 〇〇un 190.5 1956.3 62.8 5.62 0.60 〇o K 〇〇inch 198.8 1961.8 63.2 5.58 0.58 〇p 〇〇CO 173.5 1892.4 61.6 5.71 0.73 〇w cn K 〇CN1 180.1 1924.2 62.3 5.64 0.66 〇E 〇〇τ—Η 189.4 1955.7 62.9 0.61 〇tc 〇〇 Transfer point (° 〇 Tensile elasticity (N / mm2) Tensile strength (N / mm2) Elongation (%) Water absorption (%) Adhesive electrical insulation resistance (X 10,3Ω) Pencil hardness Acid and alkali resistance Sex (Please read the note on the back first Please fill in this page again)-Binding and ordering 1 ^ This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -52-524813 A7 B7 V. Description of the invention (50) (Please read the note on the back first Please fill in this page again from the results) From the results shown in Table 2, it can be seen that the hardened product of the multi-core epoxy compound of the present invention 'glass transition temperature board' has excellent mechanical strength, water absorption, adhesion, electrical insulation resistance, hardness, It also has excellent properties such as chemical resistance. On the other hand, the cured product of the aromatic epoxy compound obtained from the comparative example has a low glass transition point and poor water absorption and hardness. Synthesis Example 8 A gas introduction tube and a stirring device are provided. , A cooling tube and a flask of a thermometer, add 169 parts of 1,5-di-naphthylnaphthalene, and epoxy equivalent of 194 g / equivalent of 3,3 ', 5,5'-tetramethyl-1,4 1,130 copies of hydroxybiphenyl dipropylene oxide were printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China, and dissolved in 120 t under stirring in nitrogen. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 t: while maintaining the temperature at 150 ° C for about 90 minutes, the epoxy equivalent was 350 grams. / Equivalent epoxy compound (8). Next, the temperature in the flask was cooled to 70 ° C, and then, 8.0 parts of epichlorohydrin and 169 parts of dimethyl asus were added, and the temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed in 90 minutes, and 180% of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction was completed, the excess epichlorohydrin and dimethyl arsenic were distilled under reduced pressure at 120 ° C, 50 mm Hg, and the reaction product containing parasalt and dimethyl arsenic was dissolved in methyl isopropyl alcohol. Butyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 262 g / equivalent polynuclear epoxy compound (a-8). The obtained polynuclear epoxy compound (a-8), if calculated from the epoxy equivalent, then the alcoholic hydroxyl group in the general formula (7 a) 1.5 5 out of about 7 This paper size applies the Chinese National Standard (CNS) A4 specification ( 21〇 × 297 mm) ^ 53--524813 A7 ___B7_ 5. Description of the invention (51) .8 6 epoxidation. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 55%. (Please read the precautions on the back before filling this page.) Secondly, put 1 part of the polynuclear epoxy compound (a-8) 4 7 into a flask equipped with a stirring device, a cooling tube and a thermometer, and add carbitol acetate 4 0 〇parts, heat to dissolve and add 0.46 parts of methylhydroquinone, and 1.38 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 129 parts of acrylic acid, reaction 1 6 hours. Hereinafter, this reaction solution is referred to as b-1 lacquer. The infrared absorption spectrum of the polynuclear epoxy acrylate compound (b-1) obtained by this synthesis example (determined by FT-IR with a Fourier transform infrared spectrophotometer) and nuclear magnetic resonance spectrum (solvent c DC 1 3, reference substance TMS (four Methylsilane V is shown in Figures 3 and 4. Synthesis Example 9 5 2 8 parts of the polynuclear epoxy compound (a-8) obtained in Synthesis Example 8 were placed in a flask equipped with a stirring device, a cooling tube, and a thermometer. Add 400 parts of carbitol acetate and heat to dissolve, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly drip into the Ministry of Economic Affairs wisdom 72 copies of acrylic acid were printed by the consumer cooperative of the property bureau and reacted for 16 hours. This reaction solution is hereinafter referred to as b-2 lacquer. Synthesis Example 10 The polynuclear epoxy compound (a-3) 5 1 obtained in Synthesis Example 3 8 parts, put into a flask equipped with a stirring device, a cooling tube and a thermometer, add carbitol vinegar. Ethyl acetate 400 parts heat to dissolve, add methyl hydrogen to prepare 0.46 parts and triphenylphosphine 1. 3 8 parts , Heating at 95 to 105 ° C, slowly dripping into the paper standard applicable Chinese national standard (CN S) A4 size (210X297 mm) Γ54-'524813 A7 B7 V. Description of the invention (52) 8 parts of acrylic acid, reacted for 16 hours. This reaction solution is hereinafter referred to as b-3 lacquer. (Please read the back Please fill in this page again for preparation} Synthesis Example 1 1 Put 4 7 3 parts of the polynuclear epoxy compound (a-4) obtained in Synthesis Example 4 into a flask equipped with a stirring device, a cooling tube and a thermometer, and add carbitol acetate Dissolve 400 parts by heating, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 t, slowly add 127 parts of acrylic acid, and react for 16 hours. The reaction solution is hereinafter referred to as b-4 lacquer. Synthetic Example 1 2 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economy printed 2 7 7 copies of the polynuclear epoxy compound (a-6) obtained in Synthetic Example 6, Put in a flask equipped with a stirring device, a cooling tube and a thermometer, add 233 parts of carbitol acetate and heat to dissolve, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine. Heat at 105 ° C, slowly add 72 parts of acrylic acid, and react for 16 hours. This reaction solution is hereinafter referred to as b-6 lacquer. Compared to Synthesis Example 1, 5 2 7. Parts of cresol lacquer-type epoxy resin (Epiclon N — 6 9 5 manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 2 220 g / equivalent) was placed in the equipment. Gas introduction tube, stirring device, cooling tube and thermometer flask, add 300 parts of carbitol acetate to heat and dissolve. Add this paper to the standard of China National Standard (CNS) A4 (210X297 mm) _ 55 Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives 524813 A7 -------- B7_ V. Description of the Invention (53) Hydroquinone 0 · 4 6 parts and diphenylphosphine; [· 3 8 parts. Mix the mixture between 9 5 and 105. (: Heat, slowly drip 3 parts of acrylic acid, and react for 6 hours. This reaction solution is hereinafter referred to as b, — i 7 lacquer. Comparative Synthesis Example 2 A cresol lacquer-type epoxy resin (Epiclon N — 6 9 5. "Epoxy equivalent of 220 g / equivalent" manufactured by Daikoku Ink Chemical Industry Co., Ltd. 602 parts' is placed in a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer, and carbitol is added. 3,000 parts of acetate was dissolved by heating, 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated at 95 to 105 ° C, and 98 parts of acrylic acid was slowly added dropwise to the reaction. 16 hours. This reaction solution is hereinafter referred to as b '~ 2 lacquer. Comparative Synthesis Example 3 A phenolic lacquer-type epoxy resin (EPPN — 2 01), manufactured by Nippon Oil Chemical Co., Ltd., has an epoxy equivalent weight of 190 g. (Equivalent) 508 parts, put in a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer, add 300 parts of carbitol acetate and heat to dissolve, add 0 · 4 6 parts of hydroquinone and 1 · triphenylphosphine 38 parts. The mixture was heated at 95 to 105 t, and 192 parts of acrylic acid was slowly added dropwise and reacted for 16 hours. This reaction solution is hereinafter referred to as b-3 lacquer. Comparative Synthesis Example 4 Burning with a gas introduction tube, a stirring device, a cooling tube, and a thermometer -------- ΓΙΦ · ^ ------, order ----- (Please read the notes on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -56-524813 A7 ___ B7_ V. Description of the invention (54) ( Please read the notes on the back before filling this page) Bottle, add bisphenol A 3 1 3 parts and bisphenol A type epoxy resin (Epiclon 840, made by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 180 grams (Equivalent) 987 parts, dissolved under stirring at 120 ° C under nitrogen. Then, 65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C while maintaining the temperature at 150 ° C. The surface reaction takes about 90 minutes to obtain an epoxy equivalent of 475 g / equivalent epoxy compound (g). Next, the temperature in the flask is cooled to below 70 ° C. 'Epichlorohydrin is added 1 8 5 1 Parts, dimethyl asus 1690 parts' heated to 70 ^ with stirring: and kept. After that, disperse in 90 minutes and add 96% sodium hydroxide 110 parts. After adding After 3 hours of reaction, after the reaction, the excess of epichlorohydrin and dimethyl arsenic were distilled under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction products containing byproduct salt and dimethyl arsenic. It was washed with methyl isobutyl ketone in water, and then methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 3 36 g / equivalent epoxy compound (h). If the obtained epoxy compound (h) is calculated from the epoxy equivalent, about 0 · 9 of the alcoholic hydroxyl groups of 2 · 00 in the general formula (6) (where X = Y) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 45%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The epoxy compound (h) 4 9 4 parts were placed in a flask equipped with a stirring device, a cooling tube and a thermometer. 400 parts of carbitol acetate was added, and dissolved by heating. Add 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 106 parts of acrylic acid, and react for 16 hours. This reaction solution is hereinafter referred to as b'-4 lacquer. Examples 8 to 13 and Comparative Examples 5 to 8 i The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -57-524813 A 7 B7 V. Description of the invention (55) Use as shown in Table 3 The compounding components of each of the varnishes obtained in the above Synthesis Examples 8 to 13 and Comparative Synthesis Examples 1 to 4 were kneaded with a three-roller to obtain a photocurable and thermosetting resin composition. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210X297 mm) -58-524813 A7 B7 V. Description of the invention ) Table 3 Composition f: (parts by mass) Actual a Just Comparative Example 8 9 10 11 12 13 5 6 7 8 b-1 167-b-2 • 167------b-3--167--- ---Tree b-4---167------Fat b-5----167 '-----淸 b-6-----167----Lacquer b,- l----143---b, -2-------143--b, -3-143-1 b, -4 167 Irgacure-907 12 12 12 12 12 12 12 12 12 12 ITX 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Dicyandiamine-1-----1--KS-66 15 15 15 15 15 15 15 15 15 15 R-974 1 1 1 1 1 1 1 1 1 1 card Betanol acetate 10 10 10 10 10 10 10 10 10 10 j Barium sulfate 20 20 20 20 20 20 20 20 20 20 20 | 80 80 80 80 80 80 80 80 80 80 (Please read the precautions on the back before filling this page ) Printed Notes for Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Irgacure-907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinaminoacetone-1 (Photopolymerization initiator from Cibat Chemical Co., Ltd.) ITX: isopropyl Thioanthrone (manufactured by Nippon Kayaku Co., Ltd.) DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) KS-66: a ketone defoamer (by Shin-Etsu Chemical Co., Ltd.) 974: Micronized silicon oxide (manufactured by Japan AerosiK shares) The size of the sheep paper is applicable to the Chinese National Standard (CNS) A4 specifications < 210X297 mm) 1: 5 524813 A7 5. Description of the invention (57) The above examples and comparative examples The composition was dried at 80 t for 30 ° ^ 'exposed and hardened at an exposure amount of 500 millijoules per square centimeter', and after exposure to Example 9 and Comparative Example 6, it was at 150 °. (: Hardened for 1 hour. The glass transition point, tensile elasticity, tensile strength, elongation, water absorption, pencil hardness, electrical insulation resistance were measured in the same manner as described above, and adhesion, acid resistance, and alkali resistance were evaluated. The evaluation results are shown in Table 4. (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs This paper is scaled to the Chinese National Standard (CNS) A4 (210X 297 mm)- 60-524813 A7 B7 V. Description of the invention (58) Comparative example printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 〇〇120.4 2018.9 r—H oi \ or—H On 1 PC csi 〇wn csi 〇〇1 »" · ^ un CNl 1 ^ 2249.6 oo ON CN r — PC cn <] < 〇 \ 〇134.3 2307.5 r- r < f " 丨 丨 4 inch <] 〇ν / Ί t—H OO CN γ_ ·· Η 2293.5 ii cs CN r- ^ inch < S < 〇 Example cn r-Η 162.5 2349.5 CNj ii un ON inch · o E 〇rH cn 〇〇CN | r-Η 160.7 2340.1 to o OO CTs inch · CN E 〇CN cn 〇〇 \ ..... i! M4 160.8 1 1998.8 CNl oo un un o E \ o 〇〇〇 150.5 1920.4 m cn uo m oo o 〇VO CO 〇〇ON 167.2 2015.2 cn s inch T—t wo} i X 〇ON CN 〇〇oo 155.4 1975.7 On S un oo X 〇〇〇Characteristic an-a SP i Pull Elongation (N / mm2) Tensile strength (N / mm2) Elongation (%) Water absorption (%) Pencil hardness Adhesive electrical insulation resistance (X 10 丨 3Ω) Acid and alkali resistance I ---- --------- IT ------ 0 (Please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -61- 524813 A7 _B7_ V. Description of the invention (59) (Please read the notes on the back before filling this page) From the results shown in Table 4, it can be seen that the hardened product of the polynuclear epoxy propionate compound obtained from the present invention has a high The glass transition point is 'excellent in mechanical strength' and has excellent properties such as water absorption, adhesion, electrical insulation resistance, hardness, and chemical resistance. On the other hand, the hardened | cured material of the aromatic epoxy acrylate compound obtained from the comparative example has inferior glass transition point, water absorption, hardness, etc. Synthetic Example 1 4 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the 3 4 1 parts of the polynuclear epoxy compound (a-8) obtained in Synthetic Example 8 and put it in a bottle equipped with a stirring device, a cooling pipe and a thermometer. Add 400 parts of carbitol acetate, dissolved in the reaction, added 0.46 parts of methylhydroquinone, and 1.8 parts of triphenylphosphine, heated at 95 to 105 ° C, slowly dripped acrylic acid 9 4 parts, reaction for 16 hours. The reaction product was cooled to 80 to 90 ° C, 166 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, the oxidation and total oxidation of the reaction solution were measured by potentiometric titration. The obtained addition rate was used for tracking, and the response rate was above 95% as the end point. In this way, a carboxyl group-containing active energy ray-curable resin was obtained, and the acid content of the solid matter was 102 mg / kg. This reaction solution is hereinafter referred to as A-1 lacquer. The infrared absorption spectrum of the carboxyl group-containing active energy ray-curable resin (A-1) obtained in this synthesis example (measured by Fourier infrared spectrophotometer FT-IR) and the nuclear magnetic resonance spectrum {solvent CDC i 3, reference substance TMS (4 Methylsilane)} are shown in Figures 5 and 6, respectively. Synthetic example. 1 5 For the paper size of this paper equipped with gas introduction tube, stirring device, cooling tube and thermometer, the Chinese National Standard (CNS) A4 specification {210X297 mm) -62-524813 A7 B7 V. Description of the invention (6〇 ) Bottle, add 203 parts of 1,5-dihydroxynaphthalene and bisphenol A epoxy resin (please read the precautions on the back before filling this page) grease (Epiclon — 840, Daiyoshi Ink Chemical Industry Co., Ltd.) System, epoxy equivalent 180 g / equivalent) 1097 parts, dissolved at 120 ° C under stirring in nitrogen. Thereafter, 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 while the surface was reacted for about 90 minutes to obtain an epoxy equivalent of 3 65 grams. / Equivalent of epoxy compound (15). Next, the temperature in the flask was cooled to below 70 ° C, and 2058 parts of epichlorohydrin and 169 parts of dimethyl asus were added, and the temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed over 90 minutes, and 96% sodium hydroxide was added in 12 parts. After the addition, it was reacted for another 3 hours. After the reaction was completed, the excess epichlorohydrin and dimethyl arsenic were distilled under reduced pressure at 120 t, 50 mm Hg, and the reaction product containing parasalt and dimethyl arsenic was dissolved in methyl. Isobutyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 275 g / equivalent polynuclear epoxy compound (a-1 5). If the obtained polynuclear epoxy compound (a-5) is calculated from the epoxy equivalent, about 0.82 of the alcoholic hydroxyl groups of 1.71 in the general formula (7b) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 48%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Secondly, put 3 4 7 parts of the polynuclear epoxy compound (a-15) into a flask equipped with a stirring device, a cooling tube and a thermometer. Add carbitol acetate 4.0 parts , Heat to dissolve. Add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 91 parts of acrylic acid, and react for 16 hours. The reaction product was cooled to 80 to 90 t: 163 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. In the reaction, the paper size applies the Chinese national standard (CNS) A4 specification (210X297 mm) ~~-63-524813 A7 B7 V. Description of the invention (61) (Please read the precautions on the back before filling this page) Poor The oxidation and total oxidation of the reaction solution were determined by titration, and the obtained addition rate was used for tracking. The reaction rate was 95.5% or higher as the end point. The thus obtained residue-containing active energy line curable resin 'has a acid content of 1,000 mg of KOH / g. This reaction solution is hereinafter referred to as A-2 lacquer. Synthesis Example 16 In a flask equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, bisphenol A 2 2 parts and epoxy equivalent 194 g / equivalent 3,3,5,5'-4 were added. 1,078 parts of methyl 4,4, -dihydroxydiphenyl dipropylene oxide were dissolved at 120 ° C under stirring in nitrogen. After that, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C, while the temperature was maintained at 150 ° C. The reaction was carried out for about 90 minutes, and epoxy equivalent of 360 grams was obtained. / Equivalent epoxy compound (1 6). Next, cool the temperature in the flask to below 70 ° C, add 187 parts of epichlorohydrin and 690 parts of dimethyl arso, and heat up to 70 t under stirring: Employees' Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Print and keep. Thereafter, it was dispersed in 90 minutes, and 96% sodium hydroxide was added in 11 parts. After the addition, it was reacted for another 3 hours. After the reaction, the excess of epichlorohydrin and dimethyl arylene were distilled under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction product containing by-product salt and dimethyl arsenic in methyl isopropyl. Butyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 276 g / equivalent polynuclear epoxy compound (a-16). If the obtained polynuclear epoxy compound (a-16) is calculated from the epoxy equivalent, about 0.77 of the alcoholic hydroxyl groups of 1.5 to 4 in the general formula (6) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 50. This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm)-64-524813 A7 B7. 5. Description of the invention (62)%. (Please read the precautions on the back before filling this page.) Next, 349 parts of the polynuclear epoxy compound (a-16) are placed in a flask equipped with a stirring device, a cooling tube and a thermometer, and carbitol vinegar is added. 4 0 0 parts' heat to dissolve, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 9 1 parts of acrylic acid, and react for 16 hours . The reaction product was cooled to 80 to 90 ° C, 159 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, potentiometric titration was used to measure the oxidation and total oxidation of the reaction solution, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. In this way, the obtained active energy ray-curable resin containing a carboxyl group has a solid acidity of 98 mg / kg / g. This reaction solution is hereinafter referred to as a 3 lacquer. Synthetic Example 17 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The reaction product obtained in Synthetic Example 12 was cooled to 80 to 0 t, and 130 parts of tetrahydrophthalic anhydride was added for 8 hours. During the reaction, potentiometric titration was used to measure the oxidation and total oxidation of the reaction solution, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing active energy linear hardening resin 'thus obtained had a non-volatile content of 67%, and the acid hydration of the solid matter was 102 mg K0Η / g. This reaction solution is hereinafter referred to as a-4 lacquer. Synthesis Example 1 8 The reaction product obtained in Synthesis Example 13 was cooled to 80 ° to 0 ° C, 130 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. Potentiometric titration during the reaction. The paper size applies the Chinese National Standard (CNS) A4 specification (21 ° parent 297) 524813 A7 _ — B7_ V. Description of the invention (63) (Please read the precautions on the back before filling this page) The oxidation and total oxidation of the reaction solution were measured, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing active energy ray-curable resin thus obtained had a non-volatile content of 67%, and the acid content of the solid matter was 103 mg KOH / g. This reaction solution is hereinafter referred to as a-5 lacquer. Comparative Synthesis Example 5 A cresol lacquer-type epoxy resin (.Epiclon N — 6 95, manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 2 220 g / equivalent) 3 3 0 parts was placed in the equipment Add 400 parts of carbitol acetate to the gas introduction tube, stirring device, cooling tube and thermometer flask, heat to dissolve, add 0.46 parts of hydroquinone and 1.8 parts of triphenylphosphine. The mixture was heated at 95 to 105 ° C, 108 parts of acrylic acid was slowly added dropwise, and reacted for 16 hours. The reaction product was cooled to 80 to 80 ° C, 163 parts of tetrahydrophthalic anhydride was added, and reacted for 8 hours. During the reaction, the oxidation and total oxidation of the reaction solution were measured by potentiometric titration, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing photosensitive resin thus obtained had a solid acid acidity of 100 mg Kom / g. This reaction solution is hereinafter referred to as Beta-1 lacquer. A comparative synthesis example printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 'Place in a flask equipped with a gas introduction tube, stirring device, cooling tube, and thermometer' Add 400 parts of carbitol acetate, heat to dissolve, add hydroquinone. 0.46 This paper applies Chinese National Standard (CNS) Α4 Specifications (210X297 mm) -66-524813 Α7 Β7 V. Description of the invention (64) (Please read the precautions on the back before filling this page). This mixture was heated at 95 to 105 ° C and slowly added 122 parts of acrylic acid, and reacted for 16 hours. The reaction product was cooled to 80 to 80 ° C, 156 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, the oxidation and peroxidation of the reaction solution were measured by potentiometric titration, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing photosensitive resin thus obtained had a solid acid acidity of 96 mg K0Η / g. This reaction solution is hereinafter referred to as B-2 lacquer. Comparative Synthesis Example. 7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The polynuclear epoxy compound (h) 3 5 2 parts obtained in Comparative Synthesis Example 4 were placed in a flask equipped with a stirring device, a cooling tube and a thermometer, and the card was added. 400 parts of acetol acetate were dissolved by heating, 0.46 parts of methylhydroquinone, and 1.8 parts of triphenylphosphine were added. Heat at 95 to 105 ° C and slowly add 75 parts of acrylic acid, and react for 16 hours. The reaction product was cooled to 80 to 80 ° C, 172 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, potentiometric titration was used to measure the oxidation and total oxidation of the reaction solution, and the resulting addition rate was used for tracking. The reaction rate was 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a solid acid acidity of 106 mg KO / g. This reaction solution is hereinafter referred to as B-3 lacquer. Example 1 4 to 18 and Comparative Examples 9 to 1 1 The compounding components of each lacquer obtained in Table 5 using the above Synthesis Examples 14 to 18 and Comparative Synthesis Examples 5 to 7 were kneaded with a three-roller machine. , To obtain photo-hardenable. · Thermosetting resin composition. The characteristics of each composition are shown in the paper. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -67-524813 A7 B7 I V. Description of the invention (α) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 5 I Composition (parts by mass) Example Comparative Example 14 15 16 17 18 9 10 11 Al 167-------Α · 2-167-----Α-3--167----- Tree Α-4--149----Zhi Α-5--雠-149---Lord ί 円 Β-1-----167--Lacquer Β-2------167-Β -3 _-------167 Irgacure-907 12 12 12 12 12 12 12 12 12 ί 1 ί ΙΤχ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5! I-ί dicyandiamide 1 1 1 1 1 1 1 1 DPHA 15 15 15 15 15 15 15 15 KS-66 1 1 1 1. 1 1 1 1 40004000 4000 36 35 34 35 36 35 34 37 R-974 10 10 10 10 10 10 10 10 Carbitol acetate 20 20 20 20 20 20 20 20 Barium sulfate 80 80 80 80 80 80 80 80 Remark Υ4000: Bixylenol epoxy resin (made by Japan Epoxy Resin (stock)) (Please read the precautions on the back before filling this page) A \ — / SNC // V Standard home country Suitable sheets of paper I graduated scale • r ^ I [xi] Shu PCT well 7 9 2 X ο / b - 524813

7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (66) Table 6 Characteristic Examples Comparative Examples 14 15 16 17 18 9 10 11 Developing 40 minutes drying 50,000 50,000 drying 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 △ △ X Glass transition point 165.4 157.2 150.5 161.2 167.3 150.7 150.5 125.6 (° C) Tensile elasticity Rate 2475.7 2415.2 2390.4 2432.7 2464.1 2891.3 2820.5 2451.8; (N / mm2) Tensile strength 63.9 64.3 68.6 68.9 70.5 48.3 49.1 64.1 (N / mm2) Elongation 4.90 5.04 5.76 6.17 5.93 2.75 3.10 5.11 (%) Water absorption 0.71 0.78 0.83 0.78 0.80 1.32 1.35 1.47 (%) Pencil hardness 6H 6H 5H 6H 6H 6H 6H 2H Adhesiveness 〇〇〇〇XX 〇 Electrical insulation resistance 3.6 3.4 3.5 3.5 3.3 2.1 1.9 0.8 (X 101? Ω) i Acid resistance 〇〇〇 〇〇Δ Δ 〇 Alkali resistance 0.0000000 〇 PCT resistance 〇〇〇〇〇XX Δ (Please first Read the notes on the back and fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -69-Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 524813 A7 __B7 V. Description of Invention (67) The performance test method in Table 6 is as follows. < Developability >: The composition of each of the above Examples and Comparative Examples was fully coated by screen printing on a copper foil substrate on which a pattern was formed, and the coating was applied at 80 t at 4050, 60 or 70 minutes. After drying and cooling to room temperature, the solution was developed in 30% 丄% sodium carbonate aqueous solution at a spray pressure of 2 kg / cm 2 for 60 seconds to visually confirm the presence or absence of development residue in the dried coating film. The judgment criteria are as follows. ○: Completely developed. △: Part of the coating film remains. X: The coating film is completely retained. < Glass transfer point >: The composition of each of the above Examples and Comparative Examples was coated on a Teflon board washed and dried in advance by screen printing, and dried in a hot air circulation drying oven at 80 ° C. 40 minutes. After it was cooled to room temperature, it was exposed at an exposure amount of 500 millijoules per square centimeter, and hardened in a hot-air circulation drying furnace at 150 ° C for 60 minutes. After it was cooled to room temperature, the hardened coating film was peeled from the Teflon board to obtain an evaluation sample. The glass transition point of the evaluation sample was determined by the DM method. < Tensile elasticity, tensile strength (tensile failure strength), elongation (tensile failure strength) > A tensile-compressive tester (manufactured by Shimadzu Corporation). (CNS) A Regulation 210X297 Male Thin) -70----- · --------- IT ------ (Please read the precautions on the back before filling this page) 524813 A7 ___ _B7 ___ V. Description of the invention (68) Determine the tensile elastic modulus, tensile strength (tensile failure strength), and elongation (tensile failure extension) of the above evaluation samples. (Please read the precautions on the back before filling in this page) < Water absorption >: The composition of each of the above Examples and Comparative Examples was screen-printed on a glass plate whose quality was measured in advance, and dried in a hot air cycle The oven was dried at 80 ° C for 40 minutes. After cooling to room temperature, exposure was performed at an exposure amount of 500 mJ / cm², and the specimen was hardened at 150 ° C for 60 minutes in a hot air circulation drying oven to obtain an evaluation sample. After cooling to room temperature, determine the mass of the sample. Next, a P CT device (TABAI ESPEC HAST SYSTEM T. PC-412MD) was used to evaluate the sample at 121 ° C, 100 R. Η. After processing for 24 hours, the mass of the hardened material after processing was measured. Determine the water absorption of the hardened material using the following calculation formula. Water absorption rate = (W2 — W1) / (W1 — Wg) Among them, W 1 is the quality of the evaluation sample, W 2 is the quality of the evaluation sample after PCT treatment, and W g is the quality of the glass plate. < Pencil hardness >: Calculated based on J I S K 5 4 0 0. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs < Adhesiveness > ·· Visually judge according to I S D 0 2 0. The judgment criteria are as follows. 〇: No peeling visible △: Only slight peeling X: Fully peeling paper rule Chinese national standard (CNS) A4 specification (210 x 297 mm) ^ 71-524813 A7 _ B7 V. Description of the invention (69) Insulation >: (Please read the precautions on the back before filling out this page) On the comb electrode B test piece of I PC B_2 5 The composition of each of the above examples and comparative examples was coated with a roller made by Pilot Seiko Co., Ltd. The machine is fully coated in a hot air circulation drying oven at 80 ° C for 40 minutes. After cooling to room temperature, it is exposed at an exposure of 5000 mJ / cm2. The hot air circulation drying oven is exposed at 1 5 0 Harden for 60 minutes, the sample must be evaluated. A DC bias voltage of 500 C was applied to the comb electrode, and the insulation resistance 値 was measured. < Acid resistance test > The substrate with the same evaluation for electrical insulation was immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C for 30 minutes, and was taken out for comprehensive evaluation of the state of the coating film and adhesion. The judgment criteria are as follows. 〇: No visible change. △: Only slight changes. X: Those with swelling or swelling of the coating. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Except for a 10% by volume sodium hydroxide aqueous solution, the test was evaluated in the same manner as in the acid resistance test. < PC T resistance >: The composition of each of the above Examples and Comparative Examples was coated on a printed circuit board by screen printing, and dried in a hot air circulation drying oven at 80 ° C for 40 °. China National Standard (CNS) A4 Specification (21 × 297 mm) -72-524813 A7 B7 V. Invention Description (70) (Please read the precautions on the back before filling this page)

minute. After cooling to room temperature, exposure was performed at an exposure amount of 500 mJ / cm², and the specimen was hardened at 150 ° C for 60 minutes' in a hot air circulation drying oven to obtain an evaluation sample. After cooling down to room temperature, a PC device (TABAI ESPEC HAST SYSTEM TPC-412MD) was used for 1 to 8 hours at a pressure of 1 2 1 t: 2 to evaluate the state of the hardened film. The judgment criteria are as follows. 〇: No peeling, discoloration or dissolution. △: Any of peeling, discoloration, or dissolution. X: There are many peeling, discoloration and dissolution. From the results shown in Table 6, it can be seen that the hardened material obtained from the photocurable / thermosetting resin composition of the present invention has a high glass transition point, excellent mechanical strength, water absorption, adhesion, electrical insulation resistance, hardness, It is also excellent in chemical resistance and PCT resistance. On the other hand, the hardened | cured material of the aromatic epoxy acrylate compound obtained from the comparative example has inferior glass transition point, water absorption, hardness, PCT resistance, etc. Effect of the Invention The multi-core epoxy compound printed by the employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be thermally hardened, and the multi-core epoxy acrylate compound of the present invention can be hardened or heat-cured by irradiation with active energy rays. The hardened material has a balance of high heat resistance and toughness, excellent adhesion to the substrate, and excellent water resistance, chemical resistance, and electrical insulation. It can be advantageously used in various resists, adhesives, Injection molding agents, laminates, coatings, encapsulants, etc. can be used as starting materials for active energy ray-curable resins. This paper size applies the Chinese National Standard (CNS) A4 specification < 210X297 mm) -73-524813 A7 B7 V. Description of the invention (71) In addition, it contains the active energy ray curable resin of the present invention as the basis of the photocurable component The photocurable and thermosetting resin composition of the invention is excellent in photocurability, alkali developability, and adhesion to the substrate, and also has heat resistance, water resistance, electroless plating resistance, chemical resistance, In addition to the above-mentioned uses, the hardened products are excellent in electrical insulation, flexibility, and PCT resistance. In addition to the above-mentioned applications, they can be very advantageously used as solder resists for printed circuit boards, interlayer insulation layers of multilayer printed circuit boards, and the like. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 specification {210 X 297 mm) -74-

Claims (1)

3 in "1 丄 00 4 V 8888 ABCD, application scope of appendix 1A: Patent Application No. 90101202 Chinese Application for Patent Scope Amendment 1. August 29, 1991 Amendment 1. A multi-core epoxy compound characterized by, It is as shown in the following general formula 1) CH, -CH-CH, -0-X-0--CHi \ / L OM I-0-CHi-CH-CHt-0-X — 0 OM I • CH — CH, -0-Y · -CH. -CH-CH, 0 • · (1) Glycidyl ether naphthalene diepoxy aromatic epoxy compounds, biphenol compounds, and hydrophenolic hydroxyl groups And / or hydrogen (please read the notes on the back before filling out this page) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the aromatic rings with different X and Y tables. The X table is selected from biphenol type and bixylenol type. At least one of the groups consisting of diglycidyl ether, bisphenol-type diglycidyl ether, and propyl ether has a di-glycidyl compound in one molecule, and Y is selected from dihydroxynaphthalene and its derivatives At least one of its derivatives, bixylenol and its derivatives, bisphenol and its derivatized quinones and its derivatives, has an aromatic ring residue in a molecule of diaromatic alcohol, and M represents propylene oxide. , Methyl epoxy propyl atoms, [eta] Table integer of 1 to 20 of. 2. The polynuclear epoxy compound according to item 1 in the scope of the patent application, 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, CH * -CH 一 CHt —0 ～ 5C 一 〇Χ / 〇 OH ΌΗι 〇 · This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 524813 Α8 Β8 C8 D8 (6) Six, the scope of patent application 0H- CH. -CH-CH * -0-X—0-^ — CH. —CH—CHt η 0 where X and Y represent different aromatic rings, and X represents a group selected from biphenol type diglycidyl ether and bidimethyl Aromatic ring residues of at least one of the aromatic epoxy compounds having a diglycidyl group in one molecule of a group consisting of phenolic diglycidyl ether, bisphenol diglycidyl ether, and naphthalene diglycidyl ether Group, at least one 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 The aromatic ring residue of an aromatic alcohol having a diphenolic hydroxyl group in one molecule, η is an integer of 1 to 20. 3. The polynuclear epoxy compound according to item 1 of the scope of the patent application, which is obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (7a) with epihalohydrin, and as shown in the following general formula ( 8 a) Table, R · Re 〇H (Please read the notes on the back before filling out this page) CH »One CH One CHi One 0 / / 0 0M Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy R · Re • CH, — CH—CH i / / 0 (8 a) where R3, R4, R5, R6 represent the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and M represents epoxypropyl, Methyl epoxy propyl and / or this paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -2- 524813 A8 B8 C8 ____ D8. Patent application scope hydrogen atom, η Table 1 to 20 integer . 4. The polynuclear epoxy compound according to item 3 of the scope of patent application, wherein in the general formulae (7a) and (8a), R3 to R6 are all hydrogen atoms. 5. The polynuclear epoxy compound according to item 3 of the scope of patent application, wherein in the general formulae (7a) and (8a), R3 to R6 are all methyl groups. 6. The polynuclear epoxy compound according to item 1 in the scope of the patent application, which is obtained by reacting an alcoholic hydroxyl group with an epoxy halopropane as shown in the following general formula (7b), and as shown in the following formula (8b ), R7 Ru Re OH / r- 丨 -C-2 -C Η-C Η 2 -0——0— CH2—CH—CH2 \ / 0 Re OH I —CH2 —CH—CHR! R7- -It · 0- R] R1 Re (7b) u Aw-- (Please read the notes on the back before filling out this page) Order Re R1 0- R10 -CH2 — CH printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -CH2 i \ / 〇〇 Alkyl or halogen atom having 1 to 4 carbon atoms, R11 and R12 represent the same or different hydrogen atom, methyl group or halogenated methyl group, M represents epoxy group, .methyl epoxy group and / or hydrogen atom , Η is an integer from 1 to 20. 7 · If the polynuclear epoxy compound in item 6 of the scope of patent application, wherein in the general formulae (7b) and (8b) above, all of R7 to R1Q are hydrogen atoms, and this paper size applies the Chinese National Standard (CNS) A4 specification (21 〇 X297 mm) -3-524813 B8 C8 D8, the scope of patent application and R11 and R12 are methyl. 8 · The polynuclear epoxy compound according to any one of items 3 to 7 of the scope of the patent application, wherein in the general formulae (7a), (7b), (8a) and (8b) above, the divalent naphthalene ring residual group is 1,5 —, 1,6 —, 2,6 a 'or 2,7-substituent. 9. A thermosetting resin composition characterized by containing 1,000 parts by mass of a polynuclear epoxy compound as described in item 1, 3, or 6 of the patent application of I, and 20 to 50 parts by mass of a hardener . 1 0 · — A multi-core epoxy acrylate compound characterized by ·, as shown in the following general formula (2 a), 0Z r I ζ · —0— X —0--CH · — CH—CH »— Ο—Y—〇— OZ -CH. -CH-CH * -0-X-0--Z · · · · (2a) J η Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where X and Y tables are different. Ring, X represents at least one molecule selected from the group consisting of diphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether The aromatic ring residues of the aromatic epoxy compounds having diglycidyl groups are selected from the group consisting of dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bixylenol and its derivatives, bisphenol and Its derivatives, and at least one of the aromatic ring residues of an aromatic alcohol having a diphenolic hydroxyl group in one molecule of hydroquinone and its derivatives, the Z series are independent of each other, and the following general formula (3) or (4) a base or a hydrogen atom, and at least one of Z is a base represented by the general formula (3), and Z 'is independent of each other. The following general formula (3,) or (4') -4 is shown below. -(Please read the notes on the back first (Fill in this page again.) This paper size applies to China National Standards (CNS) A4 specification (210 × 297 mm) 524813 Α8 Β8 C8 D8 The base shown in the scope of patent application, η Table 1 to 20 integer R1 0 (3) OH R1 -CH. -C-d · · · \ / 0 (4) 0 -CH, -CH-CH * -0-C-R3 (3,) (4,) OH 〇wherein R1 represents a hydrogen atom or a methyl group And R2 represents an unsaturated monocarboxylic acid residue. 1 1 · If the multi-core epoxy acrylate compound in item 10 of the patent application scope is as shown in the following general formula (2 b), OZ (Please read the precautions on the back before filling this page) CH * -CH —CH «-0-X-0--CHt —CH—CH, —Ο—Y—0- 0 OZ -CH, -CH-CH, -0-X-0- • CHi —CH—CH, \ / 0 (2b) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where X, bisphenol propyl ether group of aromatic compounds and its derivatives, quinone and aromatic alcohols derived from aromatic compounds (4) And Y are different aromatic rings, and X represents at least one selected from the group consisting of biphenol type diglycidyl ether type diglycidyl ether, bisphenol type diglycidyl ether, and naphthalene type diepoxy in one molecule. The aromatic epoxy Y with diglycidyl is selected from the group consisting of dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bisphenol and its derivatives, and ring residues with diphenolic hydroxyl groups in the hydrogen molecule Group, bi-cresyl group formed by a ring residual group, the group or the hydrogen η Table 1 to at least one of the Z system is independent of each other, atom, and the integer of Z to 20, the following general formula (3 ) Or less (3) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -5- 524813 A8 B8 C8 D8, patent application scope 0 —〇—C — R1IOH (3) R1 I -CH, — C — \ / 0 (4) where R1 represents a hydrogen atom or a methyl group, and R2 represents an unsaturated monocarboxylic acid residue. 1 2 · The polynuclear epoxy acrylate according to item 10 of the scope of the patent application, which is shown in the following general formula (9a), R * R · 0Z • CH, -CH-CH · Z · — 0 R4 Re (9 J η wherein R3, R4, R5, and R6 are the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z are independent of each other. The following general formula (3) or (4) ) Or a hydrogen atom, and at least one of ζ is not related to the base 'Z' in the general formula (3), and the bases shown in the general formula (3 ') or (4') below are shown. , Η is an integer from 1 to 20, R1 0 —CH * —C —CHi —0 —C—R * 0H (Please read the notes on the back and fill in this page first) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 0 -CH, -CH — CH, -0-C_R * IOH R1 I (3) —CHt —C — CHi \ / 0 (3 ·) -CH * -CH-CH 嚣 \ / 0 ⑷ (4 · where R1 table A hydrogen atom or a methyl group or R2 represents an unsaturated monocarboxylic acid residual group. 1 3 · The polynuclear epoxy acrylate compound according to item 10 of the patent application scope, which is shown in the following general formula (9b). Applicable to China National Standard (CNS) A4 specification (210X297 mm) -6-524813 A8 B8 C8 D8 R · Re 0Z 0 Among them, the scope of application for the patent of the RRR is -CHi -CH-CHt -Ο -CH * — CH—CH! (9b) 0 R6 is the same or different, the surface hydrogen atom or the atomic number of 1 to 4, the Z is independent of each other, The following formulae (3) or (4) do not show a base or a hydrogen atom, and at least one of z is a base shown by general formula (3), η is an integer from 1 to 20, and R1 is CH *- C —CH, \ / 0 R1 〇I 1 -CHt-C-CHa-0-CH I OH (3) ⑷ (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R1 represents a hydrogen atom or a methyl group, and R2 represents an unsaturated monocarboxylic acid residue. 1 4. The polynuclear epoxy acrylate compound according to item 12 or 13 of the scope of patent application, wherein in the general formula (9 a) or (9b), R 3 to R 6 are all hydrogen atoms. 15 · The polynuclear epoxy acrylate compound according to item 12 or 13 of the scope of patent application, wherein in the above general formula (9a) or (9b), R3 to R6 are all methyl groups. 16 · As for the multi-core epoxy acrylate compound in the scope of the patent application No. 10, which is shown in the following general formula (9 c), this paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 524813 A8 B8 C8 D8, patent application scope V -CHi 0Z \ -CH-CH, RT Ru R · -CH, -CH-CH. -0—〇R · 1 wherein R7, R8, R9, R, an alkyl or halogen atom having 1 to 4 carbon atoms, Rll and r12 are the same or different and represent a hydrogen atom, a methyl group, or a halogenated methyl group, and Z is independent of each other. The following table shows a group or a hydrogen atom represented by the general formula (3) or (4) below, and at least one of z Z is a base represented by the general formula (3), and Z is independent of each other. The following bases represented by the general formula (3 ') or (4') are shown below. Η is an integer from 1 to 20, and R1 0 R1 ^ I » * One CH * -C-CH, — 0-CR * · I 0Η (3) • Z · (9 c) V R1 are the same or different, the surface hydrogen atom is CHa — C — CHa \ / 0%%% (4) (Please read the notes on the back before filling this page) 0 I One CH2 —CH-CH * -0-C_Rs I OH (3, -CHi ~ CH-CHa 0 (4 ·) Intellectual Property Bureau, Ministry of Economic Affairs Employee consumer cooperatives print R1 hydrogen atom or methyl group, and R2 unsaturated monocarboxylic acid residues. 1 7 · The polynuclear epoxy acrylate compound according to item 16 of the patent application scope, wherein the general formula (9 c ), R7 to RiQ are all hydrogen atoms, and R11 and R12 are both methyl groups. 1 8 · Rushen The polynuclear epoxy acrylate compound according to the patent scope Nos. 1, 2, 3 or 16 wherein the divalent naphthalene ring residue in the general formula (9a), (9b) or (9c) is 1,5-, 1, 6 —, 2, 6-, or 2, 7-substitutes. Wood and paper standards are applicable to China National Standard (CNS) A4 (210X297 mm) 8- 524813 CHa —CH—CH * * — 〇A8 B8 C8 D8, patent application scope 19 · A hardenable resin composition characterized by containing 100 parts by mass of a multi-core epoxy acrylate compound such as the patent application scope item 10, 11, 12, 13, 3 or 16; And 0. 1 to 2 0 parts by mass of a hardener and / or 0. 1 to 25 parts by mass of a photopolymerization initiator. 2 0 ·-an active energy ray hardening resin characterized by the following general formula ( 5) The intermediate reaction product (b ') of the polynuclear epoxy compound (a,) shown with an unsaturated monocarboxylic acid (c) is obtained by reacting a polyacid g (d) with OM.CH * —CH 一 CH * — ^, 0 r ^ n ϋϋ ϋ a—ϋ m —ϋ ini ϋϋ — · — n (Please read the precautions on the back before filling this page) · 0 · OM-CHa- CH-CH, —0—X, —0CHa —CH—CH, π (5) Order 0 where X ′ and Υ ′ represent different divalent aromatic rings, and M represents epoxypropyl group and methyl epoxypropyl group. And / or hydrogen atom, η represents an integer from 1 to 20, intermediate reaction product (b ') printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 〇Z1I -CH2 — CH — CH2 — 〇—Y' — 〇 一 〇 2ι I-CH — CH, O — X 'OZ /: -CH2_ CH—CH2-O -S-R2 IOH This paper size applies to Chinese National Standard (CNS) A4 (210X29 * 7 mm) 9 524813 A8 B8 C8 D8 VI. Scope of patent application_ R1 〇 Z1: One CH2 — 0h—CH2 — 〇 One R2 or hydrogen atom I 〇Η R1: hydrogen atom or methyl group, R2: unsaturated monocarboxylic acid residue [final product] 〇Z2 〇Z2 I 丨 ^ Z2 〇 一 X, — 〇CH — CH2 — 〇 — — 〇CH2 —CH — CH2 — Ο X — 0-J η 〇 7 'II-CH2-GH-CH2- 〇 一 C —R2 I ον (Please read the notes on the back before filling in this page) 2z 2 Hc onuc I 0 1 2 Hc I 1 Η V RICIO 2 R or hydrogen atom Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ο ν:-c ~ w or hydrogen atom W: polyanhydride residues R1 · · R2 j are the same as above. 2 1. A photocurable and thermosetting resin composition that can be developed with an alkaline aqueous solution, which is characterized by containing (A) 100 parts by mass of an active energy ray-curable resin such as the 20th in the scope of patent application. (B) 10 to 60 parts by mass of a photosensitive (meth) acrylate compound, (C) 0.1 to 25 parts by mass of a photopolymerization initiator, and (D) 10 to 100 parts by mass Epoxy compounds with more than two epoxy groups in one molecule The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -10-524813 A8 B8 C8 D8 6. Application for patent scope 2 2 1 to 20 parts by mass of the (E) ring for the photocurable and thermosetting resin composition of the scope of application for the patent No. 21, for the active energy ray-curable resin of 100 parts by mass Oxygen hardening catalyst. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -11-This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)