TWI325877B - - Google Patents

Description

1325877 (1) Technical Field of the Invention The present invention relates to a linear active energy ray-curable resin having both a photopolymerizable unsaturated group and a carboxyl group, and particularly a line in which a cyclohexane ring is regularly and repeatedly contained. An alkali-soluble active energy ray-curable resin. The present invention relates to an alkali-developable photocurable thermosetting resin composition and a cured product thereof using the above active energy ray-curable resin, and more particularly, to various applications, particularly The permanent mask of the printed circuit board, the interlayer insulating layer of the multilayer circuit board, etc., after being irradiated by the active energy ray, the image is formed by the dilute alkali aqueous solution, and the heat treatment after the irradiation of the active energy ray or the heat treatment Active energy ray irradiation process, or heat treatment for final hardening, can form low dielectric properties, adhesion, resistance to no plating, electrical properties, flexibility, moisture absorption and p CT (pressure cooker test) The liquid alkali of the hardened film is a photohardenable and thermosetting resin composition, and a hardening film forming technique using the composition. [Prior Art] At present, the solder resists of some consumer printed circuit boards and almost all industrial printed circuit boards are formed by image formation using ultraviolet rays from the viewpoint of high precision and high density, and heat and light are used. The illumination is used as a liquid-type solder resist for final hardening (formal hardening). Also, due to environmental concerns, the use of a dilute aqueous alkali solution as a developing solution for alkali imaging liquid soldering has become mainstream. Such an alkali-developing type solder resist using a dilute aqueous alkali solution is disclosed, for example, in Japanese Patent Laid-Open Publication No. Hei 6 1-24 3 8 69, a lacquer type phenolic epoxy compound and not (2) (2) 1325877 saturated. The reaction product of a monocarboxylic acid is a solder resist composition of an acid anhydride photosensitive resin 'photopolymerization initiator, a diluent and an epoxy compound, and the lacquer type phenolic ring is disclosed in Japanese Laid-Open Patent Publication No. Hei. The reaction product of an oxygen compound and an unsaturated monocarboxylic acid is an acid anhydride-added photosensitive resin, a photopolymerization initiator, a diluent, an ethylene triterpene or a mixture of ethylene triacetate and dicyandiamide, and a melamine resin. Composition. As such, there has been a proposal for a solder resist, and in the manufacture of an actual printed circuit board, the photosensitive component is mainly a reaction product of the above-mentioned lacquer-type phenolic epoxy compound and an unsaturated monocarboxylic acid. A solder resist composition of a photosensitive resin added with an acid anhydride has been widely used. However, such a photosensitive resin is photocurable and has excellent alkali developability, but the balance between photocurability and flexibility is difficult to satisfy. In addition, there is a tendency to shrink during hardening, and there is little toughness in stretching, and it is sometimes susceptible to cracking due to thermal shock depending on the purpose of use. Further, in recent years, as the size and thickness of electronic devices have been shortened, the solder resists have been required to have higher performance in response to the higher density of printed circuit boards. In addition, the so-called QFP (Quad Flat Package) and SOP (Small Outline Package) ic packages, which use lead frames and encapsulating resins, have recently been replaced by 1C packages using printed circuit boards and encapsulating resins. The new package is to place a metal such as solder on a single surface of a printed circuit board to which solder resistance is applied, and to directly connect a 1C wafer by wire bonding or bumping on the other side to encapsulate the structure of the resin package with a BGA (Ball Grid Array) ), CSP (wafer size package), etc. These packages can have more pins than QFPs of the same size and are easier to miniaturize. In addition, due to the self-alignment effect of the spherical solder during the assembly, the defect rate is more -5 - (3) 1325877 is low, and the introduction has been rapidly progressed. However, the long-term reliability test of the conventionally-sold commercially available pressure is applied. occur. Moreover, since the moisture absorbed by the moisture absorption portion of the solder resists is boiled and the package is cracked, the so-called popcorn phenomenon has a lack of reliability, and it is not limited to the solder resist of the road board, the substrate for which it is used, and the like. One of the objects of the present invention is to balance the flexibility and toughness of the base. Another object of the present invention is to provide excellent resistance to moisture absorption in the solder resist of a board, the properties of a multilayer circuit board, the adhesion, and the resistance to electroless plating in a 1 C package. The hardened film can be used to form a hardened liquid. In the printed circuit board of the alkali-developing type soldering resistor, the sealing pot has poor testability, and the solder resist film is peeled off. When the package is packaged, the solder resist film inside the package body and its periphery are reproducible. Such a moisture absorption resistance is long-lasting in the above-described constitutional technique, and an interlayer insulating film or the like of a general printed circuit board is produced. In the provision of high sensitivity and flexibility, the same soluble energy line curing resin. Providing, maintaining, or enhancing the characteristics of low dielectric properties, electrical characteristics, etc. required for conventional printed circuit interlayer insulating films, etc., and achieving high density of PCT (pressure cooker test) and other printed circuit boards , surface structure, thermosetting resin composition, and [description of the invention] The first aspect of the invention is in the polybasic acid anhydride (a), and the monohydric alcohol compound (b) - the molecule has less money Providing, one molecule of jade has an unsaturated double bond and a reaction product (I), a compound (II), and a 6-(4) (4) 1325877 difunctional epoxy compound (III) a reaction product (in which at least one of the above-mentioned compound (II) having a carboxyl group and a difunctional epoxy compound (ΠΙ) is a compound having no aromatic ring), which has an unsaturated group in a side chain and has a hydroxyl group at the same time and has a ring at the end. An epoxy group having an epoxy group having a terminal epoxy group reacted with an unsaturated monocarboxylic acid (c) and an active energy ray-curable resin obtained by reacting a hydroxyl group with a polybasic acid anhydride (d). a compound having at least a dicarboxy group in the molecule (Π) At least one of a group consisting of 1,2-cyclohexanedicarboxylic acid, tetrahydrofurfuric acid, hexahydrophthalic acid, hexahydroisodecanoic acid, and hexahydropyridinic acid containing no aromatic ring, particularly preferably a ring In a more suitable aspect of the hexanedicarboxylic acid, the above difunctional epoxy compound (ΙΠ) is a hydrogenated difunctional epoxy compound. Further, a second aspect of the present invention provides: (A) the active energy ray-curable resin, (B) a photopolymerization initiator, (C) a diluent, and (D) - two in a molecule The photocurable thermosetting/thermosetting resin composition which can be used for the above-mentioned epoxy group and/or oxygen-based compound (hereinafter referred to as a cyclic ether compound) can be provided in an appropriate form, and is not limited to the above components. A photocurable/thermosetting resin composition containing (E) a curing catalyst. Further, in addition to these components, a composition of (F) an active energy ray-curable resin other than the active energy ray-curable resin may be contained. The active energy ray-curable resin of the present invention is obtained by using a polybasic acid anhydride adduct of an ester-bonded alternating copolymerized linear epoxy acrylate compound, and particularly a compound having a dicarboxy group and repeating the use of cyclohexanedicarboxylic acid. Ring (5) (5) 1325877 Hexane ring, more due to the complex anhydride addition of a linear epoxy acrylate compound with ester bonding, photocuring, alkali solubility, and photocurability at low exposure. Highly balanced flexibility and toughness. Therefore, the photocurable and thermosetting resin composition of the present invention containing such an active energy ray-curable resin as a photocurable component can provide photocurability, alkali developability, and adhesion to a substrate. Excellent, at the same time low dielectric properties, water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexibility, PCT resistance and other excellent cured products. The compounding ratio of each component is not particularly limited, and it is preferable to use a photopolymerization initiator (B) 1·1 to 25 parts by mass, 0 to 5 to 20 mass, based on 100 parts by mass of the above active energy ray-curable resin (A). Preferably, the diluent (C) is 10 to 60 parts by mass, preferably 15 to 50 parts by mass, the cyclic ether compound (D) is 10 to 100 parts by mass, and if necessary, the hardening catalyst (E) is 0.1 to 20 parts by mass. The ratio. Further, if necessary, one part of the above active energy ray-curable resin (A) may be substituted, and other active energy ray-curable resin (F) may be contained. Further, in a suitable form in which lower dielectric properties are obtained, (G) a spherical porous material having an average particle diameter of 1 to 10 μm may be contained. Further, insofar as the effects of the present invention are not impaired, (H) epoxidized polybutadiene, (I) globular urethane beads, and the like may be contained as necessary. The photocurable and thermosetting resin composition of the present invention can be used as a liquid or as a dry film, and can be used in various fields, and can be used for forming an interlayer insulating film and a solder resist of a printed circuit board. Floor. In the third aspect of the present invention, the photocurable thermosetting resin composition is cured by an active energy ray and/or heated to obtain a cured product of -8-(6) 1325877, which is a suitable sample. The state provides a printing plate in which an interlayer insulating film and/or a solder resist layer are formed of the photocurable resin composition. [Embodiment] The present invention and the like have repeatedly elaborated the result of the reaction product (I) of the hair anhydride (a) with at least one unsaturated double bond and one group of the compound (b) in one molecule, at least in one molecule. The reaction product of the compound (II) with the difunctional epoxy compound (III) (wherein the above-mentioned compound having a carboxyl group (II) and the divalent compound (III) is at least one compound having no aromatic ring) An active energy ray resin (A) obtained by reacting a saturated epoxy group with a hydroxyl group, a terminal epoxy-saturated monocarboxylic acid (c), a photopolymerizable unsaturated group, and a polyvalent acid anhydride (d) to introduce a carboxyl group. a light-curable resin composition having high sensitivity and toughness and having such an energy ray-curable resin as a photocurable component can be made into low dielectric properties, adhesion, electrical resistance, electrical properties, The present invention has finally been completed in terms of flexibility, moisture absorption resistance, and resistance to PCT (pressure cooker properties, etc.), that is, the active energy ray-curable resin of the present invention, the upper resin is reacted with an unsaturated monocarboxylic acid. Introducing a photopolymerizable unsaturated group, a meta-anhydride reaction is introduced into a carboxyl group, and a photocurable and alkali-developing polymer epoxy resin is obtained by the above-mentioned components (I), (II) and a polyaddition reaction. Linear structure, especially the line containing cyclohexane ring • Hot and hard brush circuit, polyhydric hydroxy has a dicarboxy polyaddition epoxy, and its side group is tested by active thermosetting deplating without hydroxy hardening. The epoxy is more numerous, the bone (III) structure -9 - (7) 1325877, the low dielectric properties of the cured product, the adhesion to the substrate, the electroless plating resistance, the electrical properties, the resistance Excellent in wetness and PCT resistance. Hereinafter, the active energy ray-curable resin of the present invention and each component of the photocurable thermosetting composition using the above will be described in detail. First, the active energy ray-curable resin of the present invention will be described. The active energy ray-curable resin of the present invention is produced by the following processes. A polybasic acid anhydride (a), a synthesis of a reaction product (I) of at least one unsaturated double bond in one molecule and a compound (b) of an alcoholic hydroxyl group. 2 the above reaction product (I), a compound (II) having at least a dicarboxy group in one molecule, and a polyaddition reaction product with a difunctional epoxy compound (III) (wherein the above compound (II) having a carboxyl group and a difunctional ring At least one of the oxygen compounds (I π ) is a compound having no aromatic ring), and the epoxy group having an unsaturated group in the side chain and having a hydroxyl group is synthesized. (3) Synthesis of a polyfunctional acrylate resin in which an epoxy group having an unsaturated group and having a hydroxyl group in the side chain is reacted with an unsaturated monocarboxylic acid (C). 4 Synthesis of an active energy ray-curable resin in which a hydroxyl group of the above polyfunctional acrylate resin is reacted with a polybasic acid anhydride (d). First, the synthesis of the above reaction product (I) will be explained. The raw material is a polybasic acid anhydride (a)' and a compound (b) having at least one unsaturated double bond and one alcoholic hydroxyl group in one molecule, and an addition reaction is carried out according to the following conditions to obtain a reaction product (I). The obtained reaction product (I) can be represented by the following general formula (1). -10 - (1) (8) 1325877

R: CH3, H wherein R1 represents a polybasic anhydride residue, and e is an integer of 1 or 2. Further, H is a structure of a compound (b) having at least one unsaturated double bond and one alcoholic hydroxyl group in one molecule of the latter. The polybasic acid anhydride (a) is phthalic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endylenetetrahydrophthalic anhydride, methyl a dibasic acid anhydride such as tetrahydrofurfuric anhydride or tetrabromophthalic anhydride; a tribasic acid anhydride such as 1,2,4-benzenetricarboxylic anhydride; and a tetracarboxylic acid dianhydride, a naphthalene tetracarboxylic dianhydride, and a diphenyl ether tetracarboxylic acid An aliphatic or aromatic tetrabasic dianhydride such as an anhydride, butyric acid dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride or diphenyl ketone tetracarboxylic dianhydride, and the like, for example, the following general formula (2) 1,2,4-Benzene anhydride anhydride (a-Ι).

In the formula, the K diol residue is as defined in the following general formula (3).

-ch2X

O-ch2-ch—— .g

Wherein R2 represents a hydrogen atom or a methyl group, and g is an integer of 0 or 1. The 1,2,4-benzenetricarboxylic anhydride modified product (a-1) is, for example, a glycol-based diol such as ethylene-2-11-(9)(9)1325877 alcohol, diethylene glycol, propylene glycol or dipropylene glycol. a condensate of a compound with 1,2,4-benzenetricarboxylic anhydride. Commercially available products include, for example, TMGE-100, TMEG-2 00, TMEG-300, TMEG-500, TMTA-C, etc., manufactured by Shin Nippon Chemical Co., Ltd., among which tetrabasic anhydride or tribasic anhydride and the above compounds The reaction product of (b) is used as a molecular chain extender and a side chain unsaturated double bond introducing agent in the polyaddition reaction described later, and the reaction product of the dibasic acid anhydride and the above compound (b) is used as a reaction product. Molecular chain stopper. By using these in combination, the molecular weight of the resulting epoxy resin can be controlled. Further, each of the acid anhydrides may be used in combination of two or more kinds. The compound (b) having at least one unsaturated double bond and one alcohol group in the above molecule has 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4 -Hydroxyalkyl (meth)acrylates such as hydroxybutyl ester; diethylene glycol-(meth)acrylate, dipropylene glycol-(meth)acrylate, trimethylolpropane di(meth)acrylate , glycerol di(meth) acrylate, neopentyl alcohol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Further, a compound obtained by adding a cyclic ester such as e-caprolactone to the hydroxyl group of the above compound may also be used. The preferred addition ratio of ecaprolactone is 1 mol to 1 mol per mol of the above-mentioned hydroxyalkyl (meth)acrylate. These compounds may be used alone or in combination of two or more. In the present specification, "(meth)acrylate" is a generic term for acrylate and methacrylate, and the other similar performance is the same. The above polybasic acid anhydride (a), and the reaction product (I) of at least one unsaturated bis-12-(10) 1325877 bond and one alcoholic hydroxyl group compound (b) in one molecule, the polybasic acid anhydride (a) per 1 equivalent, using compound (b 1.5 equivalents, more preferably 1.0 to 1.2 equivalents. In the reaction, diluent (C) may be used. Further, it is preferred to use a catalyst to promote the reaction. Thermal polymerization of the reaction to inhibit polymerization using thermal polymerization. The agent is more preferably used. The reaction temperature is about 60 to 150 ° C, and the reaction time is 5 to 60 hours. The reaction of the above polybasic acid anhydride (a) with the compound (b) can be used, and the tertiary amine can be used. a graded amine salt, a quaternary gun salt, a triple rust dipole, a crown ether complex, and an adduct of a tertiary amine or a tertiary phosphine with a carboxylic acid phenol. The suitable amount is relative to the above. Between 0/1 and 25 mol%, 0.5 to 20 mol% is better than 15 mol%. The above reaction is in an organic solvent or no solvent, and is described later in organic solvents (C). In the presence of -2), the reaction mixing efficiency can be improved. In addition, in the above reaction, it is anti-unsaturated double gelation. It is also possible to blow air into the polymerization inhibitor, and to polymerize, for example, hydroquinone, methylparaphenylene, tetraoxyphenol, phenothimethoxazole, copper triphenylate, etc. Next, the synthesis of the above epoxy resin will be described. I), a molecule having at least two hydroxyl groups (II) and a difunctional epoxy compound (ΠΙ) as a raw material (in which one of the carboxyl group compound (II) and the difunctional epoxy compound (III) has no aromatic ring Compounds), using the known catalysts of the latter, synthetic anti-) 1.0 to later, when it is appropriate to prevent the phosphine, acid strong anhydride Ξ > 1 to the line, and then stir The bond polymerization inhibitor ruthenium or chloro compound is an epoxy resin having at least any of the alternate poly-13-(11) 1325877, an unsaturated group in the side chain, and a hydroxyl group. The obtained epoxy resin is, for example, the following general formula (4). (4) where R3 is derived from the structure of a difunctional epoxy compound, and L is a structure derived from the combination of the above-mentioned starting materials (I) and/or (Π) and/or (III) as in the following general formula (5) , (6) and (7). Further, in the repeated construction unit, the following general formulas (5), (6) and (7) are randomly combined, and at least one or more. Further, each of the structural units (5), (6), and (7) must be combined with a structural unit of the following general formula (8).

[CH^CR-JO·^ β •—O^-R^-iO-CHj-Oi-CHj-OR^-O-CHj-CH-CH,-0-i-R>-0- 〇H iH 3 ^-R4-^-0-CHs-CH-Cr-lj-0-R3-0-CHj-CH-CHj--0-?-R4-i} ^CH-C "OH .

-CHj-CH-C :-0一· (5) (6) [aij=cR-J-o-cl e I e M ··>·««·« M····«··«·· (7)

Oii OH

Wherein R1 and R3 are the same as above, R4 represents a dicarboxylic acid residue, and e is an integer of 1 or 2. In the above molecule, a compound having a dicarboxy group (Π) is less, and a specific example is 1,2-cyclohexene dicarboxylic acid. , tetrahydrofurfuric acid, hexahydrophthalic acid, hexahydroisodecanoic acid, hexahydrotereic acid, citric acid, isophthalic acid, citric acid, succinic acid, adipic acid, muconic acid, succinic acid, etc. They may be used alone or in combination of two or more. -14- (12) (12)1325877 The difunctional epoxy compound (Π I ) is, for example, a 'bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol type or a biphenol type epoxy resin. Or a mixture thereof, a bisphenol S-type epoxy resin or the like, among which hydrogenated difunctional epoxy compounds are preferred. The hydrogenated difunctional epoxy compound (III) is, for example, EPICOTE 8 2 8 manufactured by JAPAN EPOXY RESIN Co., Ltd., EPICOTE 8 3 4 ' EPICOTE 1001, EPICOTE 1004, EPICLON 84 0 manufactured by Dainippon Ink and Chemicals, Inc., EPICLON 8 5 0 , EPICLON 1 0 5 0, EPICLON 2055, manufactured by Dongdu Chemical Co., Ltd. EPITOTO YD-011, YD-013, YD-127, YD-128, DOW C Η Μ I CAL company D. E · R.

317, D.E.R. 331 ' D.E.R. 661, D.E.R. 664, CIALD SPECIALTY CHEMICALS ARALDITE 607 1 , ARALDITE 6084, ARALDITE GY 250, ARALDITE GY 260, Sumitomo Chemical Industries, Inc. SUMI-EPOXY ESA-011, ESA-

014, ELA-115, ELA-128, AER 330, AER 331, AER 661, AER 664 (all are brand names) bisphenol A type epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd.; EPICLON manufactured by Dainippon Ink Chemical Industry Co., Ltd. 8 3 0, JAPAN EPOXY RES IN 制 PI C Ο T Ε 807, EPOTOTO YDF-170, YDF-175, YDF-2004, CIBA SPECIALTY C manufactured by Dongdu Chemical Co., Ltd. AR ALD AR ARALDITE XPY 3 by ICALS 0 6 (all are brand names) bisphenol F type epoxy tree month; JAPAN EPOXY RESIN YL-6056 'YX-4000, YL-6121 (all are brand names) and other bisphenol type or biphenol type Epoxy resin or a mixture thereof: -15- (13) 1325877 EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd., etc. Bisphenol S type epoxy resin: each hydrogenated product. Among them, a hydrogenated bisphenol A type epoxy compound is preferable, and the product name "EPIC〇TE YL-6663" manufactured by JAPAN EPOXY RESIN Co., Ltd., and the product name "EPITOTO ST-2004,", "EPITOTO" manufactured by Dongdu Chemical Co., Ltd. ST-2007 ”' “EPITOTO ST-3000,, etc. Further, the hydrogenation rate of the epoxy compound is preferably from 1% to 1% by weight, and a partially hydrogenated epoxy compound or a completely hydrogenated compound of the following general formula (9) may be used. In general, when an epoxy compound having an aromatic ring is used, the obtained photocurable thermosetting resin composition tends to absorb light due to the aromatic ring during exposure, and the sensitivity tends to decrease, and the sensitivity is improved by hydrogenation. As will be understood from the examples described later, the effect of resistance to electroless gold plating can be obtained. ~0~^0~~~ (9) The above-mentioned difunctional epoxy compound (III) may be used singly or in combination of two or more. The compound (II) having at least a fluorenyl group in the above molecule is not particularly limited, and it is particularly suitable that the above formula (5) and (6) wherein R4 is a cyclohexane ring, and another monomer component (ΙΠ) Suitable for the copolymerization of hydrogenated biguanide type A epoxy compound, which is an alternating copolymerized linear epoxy resin containing a regularly repeating cyclohexane ring, which is excellent in photocuring property and highly balanced. Hardened toughness and flexibility. a catalyst for the reaction of the above reaction product (I), a compound having at least a dicarboxy group (π) in one molecule and a difunctional epoxy compound (III) - 16 - (14) (14) 1325877, epoxy The phosphines, alkali metal compounds and amines which are quantitatively reacted with the carboxyl group are preferably used alone or in combination. Further, the catalyst is poor in gelation of the alcoholic hydroxyl group produced by the reaction of the epoxy group and the carboxyl group by the reaction of the monomer component. The phosphines may be a trialkyl or triarylphosphine such as tributylphosphine or triphenylphosphine, or a salt of these and the like, and these may be used alone or in combination of two or more. The metal compound is a hydroxide, a halide, an alcoholate or a guanamine of sodium 'lithium, lithium, etc., and these may be used alone or in combination of two or more. The guanamine is aliphatic or aromatic. , a tertiary amine, a quaternary ammonium, etc. These may be used alone or in combination of two or more. Specific examples of the amines include triethanolamine, N,N-dimethine, triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide and the like. The amount of these catalysts used is preferably from 0.1 to 25 mol%, preferably from 5 to 20 mol%, more preferably from 1 to 15%, based on the epoxy group of the difunctional epoxy compound (III). Moore is even better. The reason is that the amount of catalyst used is less than 0.1 mol. /. When the reaction is uneconomical, and when it exceeds 25% of the stomach ear, the reaction is fast and difficult to control, which is not good. The above reaction product (I), the polyaddition reaction of the compound (II) having at least a dicarboxy group in one molecule with the difunctional epoxy compound (ΙΠ), is used in the amount of α mol, /3 mol, r mo When the ear is, then r / ( α + cold) > 1 ' α point Yin 0. That is, the difunctional epoxy compound (ΠΙ) has an epoxy group present at the two ends of the epoxy resin obtained by the excess of the obtained linear structure. a polyaddition reaction of a compound (I) having at least a dicarboxy group in the molecule of the above reaction product (I) with a difunctional epoxy compound (III), which is carried out in a gas stream of an inert gas of -17-(15) 1325877 or In the air, in the coexistence of the above-mentioned catalyst, it is preferably carried out at a temperature of about 50 to 200 ° C, more preferably about 80 ° C to 150 ° C. When the reaction temperature is lower than 50 ° C, the reaction is difficult to proceed. When the temperature exceeds 200 °C, the hydroxyl group of the product reacts with the epoxy group, which is easy to gel and is not preferable. The reaction time can be appropriately selected depending on the reactivity of the raw material and the reaction temperature, and is suitably about 5 to 72 hours. Next, the synthesis of the polyfunctional acrylate resin will be described. The polyfunctional acrylate resin of the present invention can be used in the epoxy resin of the linear structure prepared as described above, and the unsaturated monocarboxylic acid (c), which is described later in the organic solvent. In the presence or absence of a polymerization inhibitor such as hydroquinone or oxygen, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, 2-ethyl-4-methylimidazole In the coexistence of a reaction catalyst such as an imidazole compound or a phosphorus compound such as triphenylphosphine, it is usually produced by reacting at about 80 to 130 °C. The epoxy resin of the above general formula (4) is reacted with, for example, an unsaturated monocarboxylic acid (c) acrylic acid to obtain a polyfunctional acrylate resin of the following general formula (10). 〇 .0-1-01=03⁄4

CH OH Lt oh (10) where L and R3 are the same as above. When the above epoxy resin is produced by reacting an unsaturated monocarboxylic acid (c) to produce a polyfunctional acrylate resin, the epoxy resin is an unsaturated monocarboxylic acid with respect to 1 mol of an epoxy group contained in the resin. c) in a ratio of 0.2 to 1.3 moles, in a solvent or in a solvent-free, heated to about 60 to 150 ° C ' -18- (16) (16) 1325877 70 to 130 ° C is better, The best is to react in the presence of air. In the reaction, gelation is prevented by polymerization, and hydrogen such as methylhydroquinone or hydroquinone is used from the Kunming type: a conventional polymerization inhibitor such as benzene wax or p-toluene vinegar or the like is preferably used. Further, in order to shorten the reaction time, it is preferred to use an esterification catalyst. A acetal catalyst can be used, for example, a tertiary amine such as N,N-dimethylaniline or samarium triethylamine and a hydrochloride or a bromate thereof; tetramethylammonium chloride, triethylbenzylammonium chloride, etc. a quaternary ammonium salt; a sulfonic acid such as p-toluenesulfonic acid; a sulfonium salt such as dimethyl sulfite or methyl hydrazine; a phosphine such as triphenylphosphine or tri-n-butylphosphine; lithium chloride, lithium bromide or tin chloride (II) A conventional catalyst such as a metal halide such as zinc chloride is used. The solvent is preferably an inert solvent. As the inert solvent, for example, toluene, xylene or the like can be used. Representative examples of the above unsaturated monocarboxylic acid (C) include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, α-cyano cinnamic acid, non-styrene cinnamic acid, and the like, and (meth)acrylic acid Ester, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di(meth) acrylate, neopentyl alcohol tri(meth) acrylate, dipentaerythritol Hydroxyl-containing (meth) acrylate unsaturated dibasic anhydride adducts such as penta(meth)acrylate, phenylglycidyl (meth)acrylate, and caprolactone (meth)acrylate Wait. Particularly preferred among these unsaturated monocarboxylic acids (C) are acrylic acid and methacrylic acid. These unsaturated monocarboxylic acids (C) may be used alone or in combination of two or more. Next, the synthesis of the active energy ray-curable resin (A) of the present invention will be described. -19- (17) 1325877

The alcoholic hydroxyl group of the polyfunctional acrylate resin produced by the above reaction is reacted with a polybasic acid anhydride (d) to obtain the active energy ray-curable resin (A) of the present invention, and the amount of the polybasic acid anhydride (d) used in the reaction is Preferably, the ratio of the alcoholic hydroxyl group 1 mole to the anhydride group is from 1 to 1 mole, more preferably, the acid enthalpy of the active energy ray-curable resin is produced in the above-mentioned polyfunctional acrylate resin. 50 to 200 mg KOH/g, more preferably 50 to 120 mg KOH/g. When the acid enthalpy of the active energy ray-curable resin is less than 50 mgKOH/g, the solubility in the aqueous alkali 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 is developed independently of the exposure conditions. Therefore, for example, the polyfunctional acrylate resin of the above general formula (10) is reacted with a polybasic acid anhydride (d). The active energy ray-curable resin of the following general formula (11) can be obtained.

:Η* —C-R^-C^OH

CH 尸 CH冬〇 -R3—0-C^-CH-iH2

Wherein R1 and R3 are the same as above, and Μ has the structural units of the following general formulas (12), (13) and (14). Further, in the repeated structural unit, the following general formulas (12), (13), and (14) are randomly combined, and the following general formula (15) is required between each structural unit (12), (13), and (I4). The structural unit is combined in one. The radical "m" can be adjusted with the reaction ratio of the polybasic acid anhydride. -20- (18) (18) 1325877

Where J and R1, R3, R4, and e are the same as above. The above reaction is carried out in the presence or absence of T in the presence of an organic solvent, and is usually carried out at about 50 to 130 °Q in the presence of a nitrogen-based, oxygen-oxidation inhibitor. At this time, if necessary, it is also possible to add a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethyl benzophenone chloride, or a bismuth compound such as 2-ethyl-4-methylacetamidine, such as triphenylphosphine. A phosphorus compound or the like acts as a catalyst. The polybasic acid anhydride (d) includes methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, /, hydrophthalic anhydride, methyl hexahydrophthalic anhydride, nordecene dianhydride, and 3,6-endylenetetrahydrophthalic anhydride. An alicyclic dibasic acid anhydride such as methyl endois tetrahydrophthalic anhydride or tetrabromophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, octene succinic anhydride, and five (-21 - (19) ( 19) 1325877 Decadienyl) succinic anhydride, phthalic anhydride '1,2,4-benzenetricarboxylic anhydride, etc., aliphatic or aromatic dibasic anhydride or tribasic anhydride, or biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid An aliphatic or aromatic tetrabasic acid dianhydride such as an anhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyroic acid anhydride or diphenyl ketone tetracarboxylic dianhydride, one or more of which may be used. . Among these, an alicyclic dibasic acid anhydride is preferred. The number average molecular weight of the active energy ray-curable resin (A) of the present invention is suitably from 400 to 100,000, preferably from 900 to 20,000, more preferably from 900 to 10, more preferably 〇. When the number average molecular weight of the active energy ray-curable resin is less than 400, the obtained cured product has insufficient toughness, and if it exceeds 100,000, the development property is poor. The photopolymerization initiator (B) is, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin and benzoin alkyl ether; acetophenone Acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1·dichloroacetophenone; -Methyl-Bu[4-(methylthio)phenyl]-2-linolinylaminoacetone-1, 2-benzyl-2-yldimethylamino-1, (4·η-endolinyl) Phenyl)-butan- ketone ' N,N·dimethylamino acetophenone sulphate acetophenone; 2-methyl hydrazine, 2-ethyl hydrazine, 2-tributyl hydrazine Anthraquinones such as hydrazine and 1-chloropurine; 2,4-dimethyl-9-oxosulfanyl, 2,4-diethyl-9-oxosulfide. Mountain star, 2-chloro-9-oxo-sulfur. Mountain star, 2, 4 · diisopropyl · 9 · oxygen sulfur. Mountain star and other 9-oxo sulfur. Stars: acetophenone dimethyl acetal benzyl ketal and other ketals; benzoyl peroxide, peroxidized AI and other organic peroxides; 2,4,5-triaryl imidazole Polymer; riboflavin tetrabutyrate, bismuth benzimidazole, 2-indole benzoxazole, 2-indole benzothiazole-22 - (20) (20) 1325877 锍 compound: 2, 4, 6 - ginseng-s-triazine, 2,2,2-tribromoethanol, trihalomethylbenzene milling and other organic halogen compounds; diphenyl ketone '4,4'-bisdiethylaminodiphenyl ketone, etc. Diphenyl ketone or ketone; 2,4,6-trimethylbenzene methyl diphenylphosphine. These conventional photopolymerization initiators may be used alone or in combination of two or more, and may further contain N,N-dimethylaminobenzoic acid ethyl ester, Ν'N-dimethylaminobenzoic acid isoamyl ester, and pentyl group. A photoinitiator such as a tertiary amine such as 4-dimethylaminobenzyl ester, triethylamine or triethanolamine. In order to promote the light reaction, it is also possible to add only the (7?5-cyclopentadiene) titanium compound which absorbs in the visible light range, such as CGI- 7 8 4 (CIBA SPECIALTY CHEMICALS^ system). Optima photopolymerization initiator is 2-methyl-l-[4-(methylthio)phenyl]-2-terminallylaminoacetone-1, 2-benzyl-2-methylamino 1-(4-terinolinylphenyl)butyl-anthracene-ketone, etc., but is not limited to these, if it absorbs light in the ultraviolet or visible range, it is made of an unsaturated group such as (meth) acrylonitrile. The radical polymerizer is not limited to a photopolymerization initiator or a photoinitiator, and may be used alone or in combination. The monthly amount of the photopolymerization initiator (b) (the total amount when the photoinitiator is used) is 1 part by mass relative to the active energy ray-curable resin (a) (solid content, lower) The same) is preferably 0.1 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass. When the amount of the photopolymerization initiator is less than the above range, the irradiation with the active energy ray does not harden, or the irradiation time must be extended to make it difficult to obtain appropriate coating characteristics. On the other hand, when a photopolymerization initiator having more than the above range is added, the photocurability is unchanged and economically unsatisfactory. Next, the above diluent (C) is used, and a photopolymerizable vinyl monomer (C·1) and/or an organic solvent (C-2). -23- (21) (21) 1325877 Representative examples of the photopolymerizable vinyl monomer (C - 1 ) include hydroxyalkyl acrylates such as 2-ethyl acrylate and 2-hydroxypropyl acrylate; Mono or diacrylic acid acrylates of diols such as alcohol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N,N-dimethyl decylamine; N-methylol acrylamide, N'N - Acrylamides such as dimethylaminopropyl acrylamide; aminoalkyl propyl acrylates such as N,N-dimethylaminoethyl acrylate and Ν'N-dimethylsulfonyl acrylate a polyol such as hexanediol, trimethylolpropane, neopentyl alcohol, dinexin, hydroxyethyl isocyanurate or the like, or an ethylene oxide adduct or propylene oxide a polyacrylate such as an adduct; a phenoxy acrylate, a bisphenol fluorene diacrylate, and an acrylate such as an ethylene oxide adduct or a propylene oxide adduct of the phenol; Acrylates such as glycidyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, triepoxypropyl isomeric cyanurate, etc.; and melamine acrylate; And methacrylic esters corresponding to each of the above acrylate and the like. The organic solvent (C-2) includes ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 赛路苏, 赛赛璐苏, 丁赛职苏, carbitol, Glycol ethers such as carbaryl alcohol, butyl carbitol, propylene glycol monocarboxylic acid, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate and An ester such as an acetate compound of the above glycol ether; an alcohol such as ethanol 'propanol, ethylene glycol or propylene glycol; an aliphatic hydrocarbon such as octane or decane; petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent It is preferable that a petroleum-based solvent such as gas oil has good compatibility with the active energy ray-curable resin (A) and does not dissolve the thermosetting component cyclic ether compound (D). -24- (22) 1325877

The diluent (C) may be used singly or in combination of two or more kinds, and a suitable range thereof is preferably used. When a photopolymerizable vinyl monomer is used, 100 parts by mass of the active energy ray-curable resin (A) is used. To 60 parts by mass of '15 to 50 parts by mass, preferably more than this amount, the dryness of the touch is poor. On the other hand, 'the amount of use of the organic solvent is limited to a specific ratio' with respect to the above-mentioned active energy ray-curable resin (A) 1 〇〇 part by mass '30 to 300 parts by mass, depending on the coating method selected set up. The purpose of the use of the above-mentioned diluent (C) is that the photopolymerizable vinyl monomer (C-1) is a component which is diluted with a photosensitive component and is easily coated, and enhances photopolymerizability. The organic solvent (C-2) is prepared by dissolving and diluting the photosensitive component to form a liquid, and drying it to form a film for contact exposure. Therefore, depending on the diluent used, any exposure method using a contactless non-contact type in which the photomask is adhered to the coating film is used.

As the cyclic ether compound (D), a polyfunctional epoxy compound (D-1) and/or a polyfunctional oxygen compound (D-2) can be used.

Specifically, the polyfunctional epoxy compound (D-1) is EPICOTE 8 2 8 manufactured by JAPAN EPOXY RESIN Co., Ltd., EPICOTE 8 3 4, EPICOTE 1001, EPICOTE 1 004, EPICL0N 840, EPICLON 8 5 manufactured by Dainippon Ink and Chemicals. 0 ' EPICL0N 1 050, EPICLON 20 55, manufactured by Dongdu Chemical Co., Ltd. EPOTOTO YD-011, YD-013, YD-127 'YD-128, DOW C Η Μ ICAL ICAL D. E _ R. 317, DER 331, DER 661, DER 664, manufactured by CIBA SPECIALTY CHEMICALS, ARALDITE 607 1 , -25- (23) (23) 1325877 ARALDITE 60 8 4, ARALDITE GY2 5 0 ' ARALDITE GY 260, 3111^, manufactured by Sumitomo Chemical Industries, Ltd. 1-£?0 Father 丫£3八-〇11, £3八-014, ELA-115, ELA-128, aER 330, AER 331, AER 661, AER 664, etc. by Asahi Kasei Industrial Co., Ltd. Bisphenol A type epoxy resin; EPICOTE YL903 manufactured by JAPAN EPOXY RE SIN Co., Ltd., EPICLON 152, EPICLON 165 manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPOTOTO YDB-400, YDB-500, DOW C manufactured by Dongdu Chemical Co., Ltd. Η Ε Μ IC AL company D. E. R. 542, CIB A SPEC IALTY C Η Ε AR ALD ALD ALD ALD SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM SUM Epoxy resin; EPICOTE 152 manufactured by JAPAN EPOXY RESIN Co., Ltd., EPICOTE 154, DEN 431 manufactured by DOW CHEMICAL, DEN 438, EPICLON-730 manufactured by Dainippon Ink and Chemicals Co., Ltd. EPICLON-770, EPICLON-865, Dongdu Chemical Co., Ltd. EPITOTO YDCN-701, YDCN-704 'ARALDITE ECN 1 235, ARALDITE ECN 1 2 73' ARALDITE ECN 1 2 99, ARALDITE XPY 307, EPPN-201, EOCN-made by Nippon Kayaku Co., Ltd. 1025, EOCN-1020, EOCN-104S, RE-306, SUMI-EPOXY ESCN-195X, ESCN-220 > manufactured by Sumitomo Chemical Industries Co., Ltd. AER ECN-235, ECN-299, etc., manufactured by Asahi Kasei Kogyo Co., Ltd. Name) lacquer type phenolic epoxy resin; EPIC LOM 8 30 manufactured by Dainippon Oil Film Chemical Industry Co., Ltd., manufactured by JAPAN EPOXY RES IN PIC Ο Τ Ε 8 0 7, Dongdu-26- (24) (24) 1325877

EPITOTO YDF-170, YDF-175, YDF-2004 manufactured by Kasei Co., Ltd., ARALDITE XPY 3 06 manufactured by CIBA SPECIALTY CHEMICALS, etc. (all are brand names) bisphenol F-type epoxy resin; EPOTOTO ST-made by Dongdu Chemical Co., Ltd. 2004' ST-2007, ST-300 (trade name) and other hydrogenated bisphenol A type epoxy resin; JAPAN EPOXY. RES IN company's EPICOTE 604, Dongdu Chemical Co., Ltd. EPOTOTO YH-434, CIB A SPECIALTY C Η E Μ ICALS company ARALD IT E MY 720, Sumitomo Chemical Industries Co., Ltd. SUMI-EPOXY ELM-120 (all are brand name) epoxy propylamine epoxy resin; CIBA SPECIALTY CHEMICALS ARALDITE CY-350 (trade name) Equivalent epoxy resin; CELOXIDE 202 manufactured by DAICEL Chemical Industry Co., Ltd., ARALDITE CY 175, CY 179, etc. (all are trade names) alicyclic epoxy resin manufactured by CIBA SPECIALTY CHEMICALS; JAPAN EPOXY RESIN YL-93 3. TEN, EPPN-501, EPPN-5 02, etc. (all are trade names) trimethyl phenylmethane type epoxy resin manufactured by DOW CHEMICAL Co., Ltd.; AP1^-60 5 6 manufactured by JAPAN EPOXY RRESIN Co., Ltd. YX-4 000, YL-6121 (all are quotient Product name) Ethyl bisphenol type or biphenol type epoxy resin or a mixture of these: EBPS-200 manufactured by Sakamoto Chemical Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., manufactured by Dainippon Ink Chemical Industry Co., Ltd. Bisphenol S type epoxy resin such as EXA-1514 (trade name): bisphenol A lacquer type phenolic epoxy resin such as EPICOTE 157S (trade name) manufactured by JAPAN EPOXY RE SIN.; EPICOTE YL manufactured by JAPAN EPOXY RESIN -93 1 , ARALDITE 163 manufactured by CIBA SPECIALTY CHEMICALS, etc. (all are trade names) 4-27- (25) (25) 1325877 hydroxyethyl ethane type epoxy resin; ARALDITE PT 810 manufactured by CIBA SPECIALTY CHEMICALS, Nissan TEPIC, etc. (all are trade names), heterocyclic epoxy resin manufactured by Chemical Industry Co., Ltd.; diepoxypropyl phthalate resin such as BLENMER-DGT (trade name) manufactured by Nippon Oil Co., Ltd.: ZX- manufactured by Dongdu Chemical Co., Ltd. Tetra-glycidyl propylene oxide resin such as 1063 (trade name); ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; EXA-4750, EXA- 4700, etc. (all are brand names) epoxy resin containing naphthyl; HP-7200, HP·720 0H, etc. (both trade names) manufactured by the Ink Chemical Industry Co., Ltd. have an epoxy resin having a dicyclopentadiene skeleton; CP-50S 'CP-5 0M manufactured by Nippon Oil & Fats Co., Ltd. The product name is a glycidyl methacrylate copolymer-based epoxy resin; and a copolymerized epoxy resin such as cyclohexylmethyleneimine and propylene methacrylate, but is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, a biphenol type or a bisphenol type epoxy resin or a mixture of these is preferable. Among the above-mentioned polyfunctional oxygen compound (D-2), a representative example of a compound having two oxygen-based groups (hereinafter referred to as a dioxane) in one molecule is a dioxane of the following general formula (16).

In the above general formula (16), 'R5 represents a hydrogen atom or a fluorenyl group having 1 to 6 carbon atoms, and P is selected from a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, and has 1 to 12 carbon atoms. Linear or branched unsaturated hydrocarbons, aromatic hydrocarbons of the following formulas (17), (18), (19), (20) and (21), the following formula (26) 1325877 (the following formula ( 22) and (23) a carbonyl group-containing linear or cyclical steroid (24) and (25) a carbonyl-containing aromatic hydrocarbon divalent group

〇7) ch2-——--〇-r7-〇" (10) (19) -ch2- -ck

(21) (20) wherein R6 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group having 1 to 12 carbon atoms, and R7 represents · 0-, -S-, -CH2-, -NH-, - S〇2-'-CH(CH3)-, -C(CH3)2- or -C(CF3)2-, R8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Representative examples of the polyfunctional oxygen compound (D-2) used in the present invention include the above-described dioxane type of the general formula (16) and the like, and may be used in addition to the compound of the above-exemplified one having two oxygen-based groups in the molecule. There are three or more oxygen-based compounds in the molecule. -29- (27) 1325877 Representative examples of compounds having three or more oxygen-containing groups in one molecule are the compounds of the general formula (26). 〇 — O-CHj

Ch2-o (26) wherein R9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q is a branch of the following general formulas (27), (28) and (29) having 1 to 12 carbon atoms; An alkenyl group or an aromatic hydrocarbon of the following general formulas (30), (31) and (32). Further, the number of the functional groups bonded to the residual group Q is preferably an integer of 3 or more, and an integer of 3 to 5,000 is more preferable.

(32) A hydrogen atom in the formula, an alkyl group having 1 to 6 carbon atoms, or an aryl group. In addition to the above compounds, a compound having three or more oxygen-based groups in one molecule, an aerobic nozzle and a lacquer phenolic resin, a poly(p-hydroxystyrene), a (cardo) type bisphenol, a cup-shaped olefin, a cup-like thief An etherified product of a resin having a hydroxyl group such as a octene olefin or a sesulylene hexaoxide or the like. Further, a copolymer of an oxygen-containing D-ring unsaturated monomer and an alkyl (meth) acrylate is used. The above oxygen compound (D - 2 ) may be used singly or in combination of two or more. The cyclic ether compound (D) as described above is thermally hardened to improve the adhesion of the solder resist -30- (28) 1325877, heat resistance and the like. The blending amount is preferably 10 parts by mass or more, more preferably 1 part by mass or less, and more preferably 25 to 60 parts by mass per 100 parts by mass of the active energy ray-hardenable resin (A). When the amount of the cyclic ether compound (D) is less than 10 parts by mass, the hygroscopicity of the cured film is high and the PCT resistance is liable to decrease. Further, the solder heat resistance and the electroless plating resistance are liable to be deteriorated. On the other hand, if it exceeds 100 parts by mass, the development of the coating film, the electroless plating resistance of the hardened film are deteriorated, and the PCT resistance is also deteriorated. The above curing catalyst (E) has, for example, imidazole '2-A Imidazole, 2-ethaneizazole, 2-ethyl-4-methimidazole, 2-benzimidazole, 4-benzimidazole '1·cyanoethyl-2-benzimidazole, 1-(2-cyanoethyl)-2 -Imidazole derivatives such as ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino) hydrazine, N-dimethylbenzylamine, 4-methoxy- Anthracene, anthracene-dimethylbenzamine, 4-methyl-anthracene, anthracene-dimethylbenzylamine or the like; an anthracene compound such as hexamethylenediamine or fluorene; a phosphorus compound such as triphenylphosphine; Further, there are, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (all of which are trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industrial Co., Ltd., manufactured by SANAPRO; 1 -CAT3 503X, U- CAT3502X (all are dimethylamine blocked trade names of isocyanate compounds), DBU, DBN, U-CATSA 102, U-CAT 5 0 02 (both bicyclic guanidine compounds and salts thereof). The present invention is not limited thereto, and the curing catalyst of the cyclic ether compound or the reactor which promotes the cyclic ether group (epoxy group, oxygen group) and the carboxyl group may be used singly or in combination of two or more kinds. Indoleamine, acetamide, benzoguanamine, melamine, 2'4-diamino-6-methylpropenyloxyethyl-S_three tillage, 2_ Vinyl 2 '4-diamino-S-triazine, 2-vinyl-4' 6-diamino-S-Sanchajing.iso-31 - (29) (29)1325877 Cyanuric acid An S-triazine derivative such as an adduct may also be used, and a compound having the function of the adhesion imparting agent and the above-mentioned curing catalyst are preferably used. i: The amount of the hardening catalyst (E) may be a usual amount, for example, 100 parts by mass or so of the above-mentioned active energy ray-curable resin (A), 0.1 to 20 parts by mass, and 0.5 to 15.0 parts by mass. good. The photocurable thermosetting resin composition of the present invention may contain an active energy ray-curable resin (F) other than the active energy ray-curable resin (A), insofar as the effects of the present invention are not impaired. The other active energy ray-curable resin (F) is required to have only an unsaturated group and a carboxyl group, and is not particularly limited. Among them, the following resins are preferred. (1) a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond, a carboxyl group-containing photosensitive resin (2) obtained by pendant addition of an ethylenically unsaturated group, having an epoxy group and an unsaturated double bond a copolymer of a compound and a compound having an unsaturated double bond, which is reacted with an unsaturated carboxylic acid, and which is obtained by reacting a secondary hydroxyl group to form a carboxyl group-containing photosensitive resin (3) having an unsaturated double bond and having an acid anhydride A copolymer of a compound having an unsaturated double bond, which is a carboxyl group-containing photosensitive resin (4) obtained by reacting a compound having a hydroxyl group and an unsaturated double bond, and an epoxy compound which is reacted with an unsaturated acid to form a secondary hydroxyl group as a polybasic acid anhydride. Reaction of the carboxyl group-containing photosensitive resin (5) The carboxyl group-containing resin obtained by reacting a polymer having a base group with a polybasic acid anhydride, and a carboxyl group-containing photosensitive resin obtained by reacting a compound having an epoxy group and an unsaturated double bond -32- (30) (30)1325877 (6) A polyfunctional oxygen compound is obtained by reacting an unsaturated monocarboxylic acid with a modified oxygen D-denier resin, and a carboxyl group-containing photosensitive resin obtained by reacting a primary hydroxyl group with a polybasic acid anhydride. (7) Multinuclear epoxidation Among the photosensitive resin containing a carboxyl group obtained by reacting a compound with an unsaturated monocarboxylic acid and reacting a hydroxyl group of a product with a polybasic acid anhydride, in order to improve the heat resistance of the obtained cured product, it is particularly preferable to use cresol oxime. An active energy ray-curable resin obtained from a lacquer type phenolic epoxy compound. Further, the photocurable thermosetting resin composition of the present invention can be blended with a spherical porous material so as not to deteriorate the properties such as coating properties and heat resistance, and the dielectric constant and dielectric tangential drop of the cured product. Quality material (G). The material of the spherical porous material (G) is cerium oxide or a crosslinked resin. When the photocurable and thermosetting resin composition is blended with a crucible, the dielectric constant and dielectric tangent of the cured product depend on the dielectric constant of the dip, and the dielectric tangent is combined with the spherical porous crucible. , because its pores contain air, it can reduce its dielectric properties. In order to be such that air is contained, the average particle diameter of the spherical porous material is preferably from 1 to 15 μm to 1 to 1 μm, and the spherical porous material is preferably from about 50 to 800 m 2 /g. The blending ratio of the spheroidal porous material (G) to 200 m 2 /g is preferably 5 parts by mass or more per 100 parts by mass of the active energy ray-curable resin (A), and 100 parts by mass. Hereinafter, it is preferably 50 parts by mass or less. The photocurable and thermosetting resin composition of the present invention can be blended with epoxidized polybutadiene (H) in order to impart flexibility and toughness. The epoxidized poly-33-(31)(31)1325877 butadiene (Η) has, for example, EPOLEAD PB 3 6 00, PB47〇0, etc. of D AICEL Chemical Industry, and the amount thereof is preferably the above active energy ray-curable resin. (A) 5 to 50 parts by mass per 100 parts by mass. In order to impart flexibility and low warpage, spherical urethane beads (I) having an average particle diameter of 1 to 15 μm may be blended. The amount of the spherical urethane bead (I) is preferably 5 to 1 part by mass per 100 parts by mass of the above active energy ray-curable resin (A). The photocurable *thermosetting resin composition of the present invention may further contain barium sulfate, barium titanate, cerium oxide powder 'fine powder cerium oxide, amorphous cerium oxide, crystalline cerium oxide, molten cerium oxide, and ball if necessary. The conventional inorganic materials such as cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and the like are used alone or in combination of two or more. These are used to suppress the hardening shrinkage of the coating film to improve the properties such as adhesion and hardness. The amount of the active material of the above-mentioned active energy ray-curable resin (A) is preferably from 10 to 300 parts by mass, more preferably from 30 to 200 parts by mass, per part by mass of the active energy ray-curable resin (A). The composition of the present invention may further contain conventionally used chromogens, hydroquinone, hydrogen, etc., such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and the like. Commonly used thermal polymerization inhibitors such as trimethyl butyl catechol, pyrogallol, alum, etc., commonly used tackifiers such as fine powder yttria, organic bentonite, microcrystalline kaolinite, An antifoaming agent such as a polyfluorene, a fluorine-containing or a polymer, and/or a flattening agent, a conventionally used additive such as an imidazole-based, a thiazole-based or a triene-based decane coupling agent are blended. The photocurable thermosetting resin composition of the present invention is the above (A), (B), (c), (D), (E) ' (F), (G), -34 - (32) (32) 1325877 (Η) and (.I) components, and, if necessary, inorganic materials, the above other compounding components are preferably blended in the above ratio, uniformly mixed, dissolved, dispersed, etc. by a roll machine or the like. The composition of the present invention is usually in the form of a liquid or a dry film. For the production of a dry film, for example, after coating the above-described composition of the present invention on a base film (release film) by a roll coater, a bar, a wire bar method, a dipping method, a spin coating method, a gravure method, and a doctor blade method, Drying in a drying oven set at 60 to 100 ° C, removing a specific amount of the diluent (C), and if necessary, posting it with a release film or the like. Accordingly, the thickness of the base film epithelial film is adjusted to 5 to 160 μm, preferably 1 to 60 μm. The base film is preferably a film of polyethylene terephthalate or polypropylene. The photocurable thermosetting resin composition of the present invention having the above composition can be diluted as necessary to adjust the viscosity suitable for the coating method, for example, a printed circuit board on which a circuit is formed by screen printing, curtain coating, or spray coating. By coating by a roll coating method or the like, the organic solvent contained in the composition is volatilized and dried at, for example, about 60 to 100 ° C to form a coating film. The dry film can only be laminated. Then, through the formation of the pattern of the mask, the active energy line is selectively exposed, and the unexposed portion is developed with a dilute aqueous solution to form a photoresist pattern, and the active energy line is further heated or hardened by the active energy line. Irradiation, or only heat hardening for final hardening (formal hardening), forming low dielectric properties, adhesion, electroless plating resistance, electrical properties, flexibility, moisture absorption resistance and resistance to PCT (pressure cooker test) Hardened film (welding resist film). The above aqueous alkali solution may be used for photohardening irradiation by using an aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, amines, etc., in the range of -35-(33) (33) 1325877. Suitable light sources include low-pressure mercury lamps, medium-pressure mercury lamps, commercial pressure mercury lamps, super-pressure mercury lamps, gas lamps or _ metal lamps. In addition, active energy lines such as laser light can also be used. When the interlayer insulating film layer of the multilayer printed circuit board is formed by using the photocurable thermosetting resin composition of the present invention, if necessary, it is adjusted to a viscosity suitable for the coating number method, for example, a conductor of a circuit board in which a circuit is formed in advance. The layer is applied by a conventional method as described above, and if necessary, dried at a temperature of, for example, about 60 to 100 to form a non-stick coating film. The dry film can only be combined in multiple layers. Then, the negative film formed by forming a opaque portion having a specific shape such as a black circle is selectively exposed by active light, and the unexposed portion is developed by, for example, the above-described alkali aqueous solution to form a black hole corresponding to the negative film. Then, if necessary, the opening of the interlayer via hole is formed, and then roughening treatment is performed with a roughening agent such as an oxidizing agent, an alkali aqueous solution or an organic solvent, and the surface of the roughened insulating resin layer is coated with electroless plating, plating, or the like. The conductor layer is then subjected to heat treatment to increase the crosslinking density of the insulating resin layer while stress relaxation. For example, it is heat-hardened at a temperature of about 140 to 180 ° C to form an interlayer having excellent properties such as impact resistance, heat resistance, solvent resistance, acid resistance, moisture absorption resistance, PC T resistance, adhesion, and electrical properties. Insulating resin layer. Then, in a usual manner, the conductor layer on the surface of the insulating resin layer is etched to form a specific circuit pattern, and a conductor layer having a circuit is formed. This operation is repeated in the desired order, and the insulating resin layer and the conductor layer of the specific circuit pattern can be alternately stacked. The photocurable thermosetting resin composition of the present invention is not limited to the insulating resin layer of the method for producing a multilayer printed wiring board by the above-described stacking method, and can also be used for, for example, multilayer printing of a copper foil layer coated with a resin. Electric-36- (34) (34) 1325877 The formation of an insulating resin layer for the production of a road board, an insulating resin composition for a film by a lamination pressing method, or the like. The present invention will be specifically described by the following examples and comparative examples. The following examples are merely illustrative, and the invention is of course not limited to the following examples. The following "parts j and "%" are based on mass unless otherwise stated. Synthesis Example 1 Feeding 1,2,4-benzenetricarboxylic anhydride to a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer 192 parts, 161 parts of hydroxyethyl acrylate and 0.4 parts of the thermal polymerization inhibitor methotrexate were reacted at 95 ° C for 12 hours to obtain an adduct (I) benzene-1,2,4-tricarboxylic acid 1-(2- Propylene methoxyethyl ester. Secondly, 1-(2-propenyloxyethyl) benzene-1,2,4-tricarboxylic acid was fed into a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer. 154 parts of ester, 172 parts of hexahydrononanoic acid and 5,000 parts by weight of hydrogenated bisphenol diglycidyl ether ("Ji-6663" by JAPAN EP0XY RESIN), in nitrogen The mixture was stirred at 10 ° C. Then 5.2 parts of triphenyl scales were added, the temperature in the flask was raised to 150 C, and the reaction was maintained at 150 ° C for about 90 minutes to obtain an epoxy equivalent of 1326 g / equivalent of epoxy. Resin. 663 parts of the obtained epoxy resin was placed in a flask equipped with a stirring device, a cooling tube and a thermometer, 'carbazone acetate 370 parts' heating Solution 0.46 parts of hydroquinone, heated at 95 to 105 ° C. Slowly drip 36 parts of acrylic acid and react for 20 hours of a multi-functional acrylate resin. Cool the polyfunctional acrylate resin to 80 to 90 ° C. 'Addition of tetrahydrofuran anhydride 1 5 2 parts' reaction for 8 hours -37- (35) (35)1325877. The reaction was titrated by potentiometric titration for the oxidation of the reaction solution, and the total oxidation was traced to obtain the addition rate of 95%. The above is the end point. The thus obtained carboxyl group-containing active energy ray-curable resin has a solid acid strontium of 65.9 mg KOH/g. The reaction solution is hereinafter referred to as enamel paint A-1. Synthesis Example 2 is equipped with a gas introduction tube, The flask of the stirring device, the cooling tube and the thermometer was fed with 154 parts of 1-(2-propenyloxyethyl) benzene-1,2,4-tricarboxylic acid obtained in the above Synthesis Example 1, and 172 parts of hexahydrofurfuric acid. And bisphenol A diglycidyl ether (manufactured by JAPAN EPOXY RESIN Co., Ltd., "EPICOTE 8 2 8"), and an epoxy equivalent of 189 g/eq., 7 6 5 parts, stirred at 1 ° C under a nitrogen atmosphere, and then added. 5.2 parts of triphenylphosphine, the temperature in the flask was raised to 150 ° C, the temperature was maintained at 1 ° C - the surface reaction was about 90 minutes An epoxy resin having an epoxy equivalent of 1082 g/eq. was obtained. 541 parts of the obtained epoxy resin was placed in a flask equipped with a stirring device, a cooling tube and a thermometer, and 3,700 parts of carbitol acetate was dissolved by heating. Add 0.46 parts of hydroquinone, heat at 95 to 105 ° C, slowly add 36 parts of acrylic acid, and react for 20 hours of the multi-functional acrylate resin. Cool the polyfunctional acrylate resin to 80 to 90 ° C, add 152 parts of tetrahydrofurfuric anhydride were reacted for 8 hours. The reaction system was titrated by a potential difference for oxidation and total oxidation of the reaction solution, and the addition rate was traced, and the reaction rate was 95% or more. The carboxyl group-containing active energy ray-curable resin thus obtained had a solid acid cerium of 77.0 mg KOH/g. The reaction solution is hereinafter referred to as enamel paint A-2. -38- (36) (36) 1325877 Synthesis Example 3 A flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer was fed with benzene-1,2,4-tricarboxylic acid 1-(1) as in the above Synthesis Example 1. 2· propylene methoxyethyl ester I54 parts, 166 parts of citric acid and 250 g/eq of hydrogenated bisphenol A diglycidyl ether (manufactured by JAPAN EPOXY RESIN, “YL-6663 ”) 1000 The mixture was stirred at i〇〇 ° C under a nitrogen atmosphere, and then 5.2 parts of triphenylphosphine was added. The temperature in the flask was raised to 150 ° C, and the temperature was maintained at 150 ° C for about 90 minutes to obtain an epoxy equivalent. 1320 g / equivalent epoxy resin. 6 6 parts of the obtained epoxy resin was placed in a flask equipped with a stirring device, a cooling tube and a thermometer, and 370 parts of carbitol alcohol acetate was dissolved by heating, and 0.46 parts of methyl hydrazine was added thereto, and heated to 95 to 105. After heating at ° C, 36 parts of acrylic acid was slowly dropped, and the reaction was carried out for 20 hours with a polyfunctional acrylate resin. The polyfunctional acrylate resin was cooled to 80 to 90 ° C, and 4 parts of tetrahydrophthalic anhydride was added, and the reaction was carried out for 8 hours. The reaction system was titrated by potentiometric difference for oxidation and total oxidation of the reaction solution, and the addition rate was traced, and the reaction rate was 95% or more as the end point. The carboxyl group-containing active energy ray-curable resin thus obtained had a solid acid bismuth of 66.2 mg KOH/g. The reaction solution is hereinafter referred to as enamel A-3. Comparative Synthesis Example 1 A flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer was fed with benzene-1,2,4-tricarboxylic acid 1 (2-propenyloxyethyl) as in the above Synthesis Example 1. 154 parts of ester, 166 parts of citric acid and 189 g/eq of bisphenol A diglycidyl ether (JAPAN EPOXY RESIN-39-(37) (37) 1325877, "EPICOTE 828") 756 The mixture was stirred at 100 ° C under a nitrogen atmosphere. Then, 5 · 2 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the temperature was maintained at 150 ° C for about 90 minutes to obtain an epoxy equivalent of 1 0 76 g / equivalent of epoxy resin. . 5 3 parts of the obtained epoxy resin was placed in a flask equipped with a stirring device, a cooling tube and a thermometer, and 3,70 parts of carbitol alcohol acetate was dissolved by heating, and methyl hydrazine was added. 4 6 parts, heated to 9 At 5 to 10 5 ° C, 3 6 parts of acrylic acid was slowly added dropwise, and the reaction was carried out for 20 hours with a polyfunctional acrylate resin. The polyfunctional acrylate resin was cooled to 80 to 90 ° C, and 15 2 parts of tetrahydrophthalic anhydride was added, and the reaction was carried out for 8 hours. The reaction was titrated by a potential difference for the oxidation and total oxidation of the reaction solution, and the addition rate was traced, and the reaction rate was 95% or more. The carboxyl group-containing active energy ray-curable resin thus obtained had a solid acid cerium of 81.3 mg KOH/g. The reaction solution is hereinafter referred to as enamel B-1. Comparative Synthesis Example 2 330 parts of cresol crequer type phenolic epoxy resin (EPICLON N-695, manufactured by Dainippon Ink and Chemicals Co., Ltd., epoxy equivalent 220) was placed in a gas introduction tube, a stirring device, a cooling tube, and a thermometer. The flask, 400 parts of carbitol acetate, was dissolved by heating, 0.46 parts of hydrogenated hydrazine and 1.38 parts of triphenylphosphine. The mixture was heated to 95 to 1 Torr 5 ° C, and 8 parts of acrylic acid was slowly added dropwise thereto for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 13 parts of tetrahydrophthalic anhydride was added, and the reaction was carried out for 8 hours. The reaction system is titrated by potentiometric difference as the oxidation and total oxidation of the reaction liquid, and the obtained addition rate is traced, and the reaction rate is 95% or more as the end point. Thus, the carboxyl group-containing photosensitive resin thus obtained, the solid acid lanthanide system 1 0 0 - 40 - (38) 1325877 mg KOH / g. The reaction solution is hereinafter referred to as enamel paint B-2. Examples 1 to 3 and Comparative Examples 1 and 2 The respective components obtained in the above Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2 were kneaded by a three-roll mill according to the components of Table 1, and photohardenability and thermosetting were obtained. Resin composition. The characteristics of each composition are shown in Table 2.

-41 - (39)1325877 Table 1 Composition Examples Comparative Example (parts by mass) 1 2 3 1 2 A- 1 143.5 A-2 150.8 Paint A-3 143.7 B- 1 15 3.6 B-2 166.7 Irgacure 369" 4.0 4.0 4.0 4.0 4.0 Melamine 2.0 2.0 2.0 2.0 2.0 DPH A2) 15.0 18.0 18.0 18.0 18.0 EPICLON N- 6 9 5 3) 3 1.7 3 7.0 3 1.8 39.1 48.1 Barium Sulfate 100.0 100.0 100.0 100.0 100.0 Phthalocyanine Green 1.0 D 1.0 1.0 1.0 1 .0 carbitol acetate 5.0 5.0 5.0 5.0 5.0 Preparation of photopolymerization initiator for nCIBA SPECIALTY CHEMICALS: 2-benzyl-2-dimethylamino-1-(4_ phenyl phenyl) )-butan- ketone 2) dipentaerythritol hexaacrylate 3) cresol phenolic phenolic epoxy resin - 42 - (40) 1325877 Table 2 Characteristic example Comparative example 1 2 3 1 2 Sensitivity 100 mJ/cm 2 6 4 5 3 2 200 mJ/cm 2 7 6 6 4 Λ 300 mJ/cm 2 8 7 7 5 4 Tensile modulus [billion kPa] 2.5 2.5 2.6 2.6 3.7 Tensile strength [million Pa] 65 68 65 57 58 Rate [%] 4.4 5.1 3.7 2.8 2.6 Water absorption rate [%] 1.1 1 .2 1 .2 1.3 1.4 Dielectric ratio 3.2 3.3 Λ . J . J 3.5 3.5 Dielectric tangent 0.020 0.025 0.023 0.028 0.030 Electrical insulation U1013 ohm) 2.2 2.0 2. 1 2.2 1 .3 PCT resistance 〇〇〇〇 Δ 4Hf /«w Electrolytic gold plating 〇〇〇 Δ Δ The performance test method in Table 2 above is as follows〇

(1) Sensitivity The composition of each of the above examples and comparative examples was completely applied to a glass epoxy substrate by screen printing, dried at 80 ° C for 20 minutes, and after cooling to room temperature, a stepper piece made of KODAK was used. 2 (21-segment) mask, exposed by OAK (the metal halide lamp 7 kW) is exposed under reduced pressure (365 nm wavelength ultraviolet light integrated light meter 1 〇〇 to 3 〇〇 mJ/square Centimeter) 'Use a 10% sodium carbonate aqueous solution at 30 °C to spray 2 kg/cm 2 -43- (41) (41) 1325877 points for 60 seconds, visually confirm the gloss of the hardened coating film. number. The higher the number of glossy segments, the higher the sensitivity. (2) Tensile modulus, (3) Tensile strength (tensile failure strength), (4) Elongation (tensile failure elongation) An evaluation sample prepared by the following method to stretch a compression tester (Shimadzu In the production facility, the tensile modulus, the tensile strength (tensile breaking strength), and the elongation (tensile elongation at break) were measured. The composition of each of the above Examples and Comparative Examples was applied by screen printing to a TEFLON plate which had been previously washed with water and dried, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After cooling to room temperature, it was exposed to an exposure amount of 00 mJ/cm 2 and hardened at 150 ° C for 60 minutes in a hot air circulating drying oven. After cooling to room temperature, the hard coating film was peeled off from the T E F L Ο N plate to evaluate the sample. (5) Water absorption rate The composition of each of the above Examples and Comparative Examples was applied by screen printing to a glass plate having a mass measured in advance, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After cooling to room temperature, it was exposed to an exposure amount of 100 mJ/cm 2 and hardened in a hot air circulating drying oven at 150 ° C for 60 minutes to evaluate the sample. The quality of the evaluation sample was determined after cooling to room temperature. Next, the evaluation sample was treated with a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC-412 MD) at 121 ° C, 100% RH for 24 hours, and the mass of the cured product after the treatment was measured, and the water absorption rate of the cured product was determined according to the following formula - 44 - (42) (42) 1325877 Water absorption = (W2-W1) / (Wl-Wg) where W1 is the quality of the sample, W2 is the quality of the sample after PCT treatment, and Wg is the quality of the glass. (6) Dielectric ratio and dielectric tangent: Calculated according to JIS Japanese gold 64 8 1. (7) Comb-type electrode B piece with electrical insulation in IPC B-25, the composition of each of the above examples and comparative examples was completely coated with a PILOT Seiko (roller) roll coater, and a hot air circulating drying oven was used. Dry at 0 °C for 30 minutes. After cooling to room temperature, it was exposed to an exposure amount of 1 毫 0 mJ/cm 2 and hardened in a hot air circulating drying oven at 150 ° C for 60 minutes to obtain an evaluation sample. A bias voltage of DC 500 volts was applied to the comb-type electrode to measure the insulation resistance 値. (8) PCT resistance The composition of each of the above Examples and Comparative Examples was applied by screen printing to a printed circuit board, which was dried by hot air circulation and dried at 80 ° C for 30 minutes. After cooling to room temperature, exposure was carried out under the conditions of an exposure amount of 100 mJ/cm 2 , and the sample was evaluated by hardening in a hot air circulating drying oven at 150 ° C for 60 minutes. After cooling to room temperature, it was treated with a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC-412 MD) at 121 ° C under 2 atm for 168 hours, and the state of the hardened film was evaluated. The judgment criteria are as follows. -45 - (43) (43) 1325877 〇: No peeling, discoloration or dissolution. △: There is any one of peeling, discoloration, and dissolution. X: There are many peeling, discoloration and dissolution. (9) Electroless gold plating resistance The compositions of the above respective Examples and Comparative Examples were applied to a printed circuit board by screen printing, and dried by hot air circulation drying at 80 ° C for 30 minutes. After cooling to room temperature, it was exposed to an exposure amount of 100 mJ/cm 2 and hardened in a hot air circulating drying oven at 150 ° C for 60 minutes to obtain an evaluation sample. The obtained evaluation sample was immersed in an acidic degreasing liquid (Japan MACDA ΜIT 'METEX L-5B 20% by volume aqueous solution) at 30 ° C for 3 minutes, then washed with water, and then immersed in a 14.4% by weight aqueous solution of ammonium persulfate for 3 minutes at room temperature. After washing with water, it was immersed in a 1% by volume aqueous solution for 1 minute at room temperature. Next, the evaluation substrate was immersed in a catalytic solution at 30 ° C (10 vol% aqueous solution of METAL PLATE ACTIVATOR 350 manufactured by MELTECS) for 5 minutes, then washed with water, and immersed in a nickel plating solution at 85 ° C (MELTELATE, MELPLATE N i - 8 6 5 Μ 2 0 vol% aqueous solution, p Η4 _ 6 ) After nickel plating for 3 minutes, it was washed with a 10 volume% sulfuric acid aqueous solution at room temperature for 1 minute. Next, the immersion evaluation sample was immersed in a gold plating solution (manufactured by MELTECS, 15% by volume of OUROLECTROLES UP and a 3 vol% aqueous solution of potassium cyanide, PH6) at 30 ° C for 30 minutes, then subjected to electroless gold plating, washed, and soaked. Rinse with running water at 60 °C for 3 minutes. The obtained gold-plated evaluation sample was adhered to the cellophane adhesive tape to confirm the state at the time of peeling. The judgment criteria are as follows. -46 - (44) (44) 1325877 〇: There are no abnormalities. △: Several peelings occurred. X: Exfoliator. As is apparent from the results of Table 2, the cured product of the photocurable resin composition of the present invention has excellent dielectric properties, water absorption, adhesion, electrical insulating resistance, hardness, and drug resistance. Excellent resistance to PCT resistance. On the other hand, Comparative Example 1 using an active energy ray-curable resin prepared by using a difunctional carboxyl group-containing compound (II) having an aromatic ring and a polyfunctional epoxy compound (III) has poor sensitivity and electroless gold plating resistance. On the other hand, in Comparative Example 2, which uses an active energy ray-curable resin prepared by using a cresol crequer type phenolic epoxy resin as a starting material, sensitivity and resistance to electroless gold plating are poor, and water absorption resistance to PCT is also poor. . From the comparison of the sensitivity results of Examples 1 to 3 and Comparative Examples 1 and 2 of Table 2, it was found that the photocurable and thermosetting resin compositions of Examples 1 to 3 were superior in sensitivity to the light of Comparative Examples 1 and 2. The curable and thermosetting resin composition requires only a low exposure amount for the same light hardening degree, and is excellent in energy cost and workability. (Industrial Applicability) The photocurable and thermosetting resin composition of the present invention has excellent photo-curability, alkali developability, adhesion to a substrate, and low dielectric properties. It is an excellent hardened material such as water resistance, electroless plating resistance, chemical resistance, electrical insulation, flexibility, and PCT resistance. It can be used as a coating, printing ink, adhesive, various resist materials, and color filter. The material used for the light sheet, etc. -47-(45)1325877, especially for the soldering resistance of printed circuit boards, and the interlayer use of the multilayer printed circuit board. -48 -

Claims (1)

(1) (1) 1325877 Picking up, patent application scope 1 - an active energy ray-curable resin, which is a polybasic acid anhydride (a) and a compound (b) having at least one unsaturated double bond and one alcoholic hydroxyl group in one molecule Reaction product (I), a polyaddition reaction product of a compound (II) having at least a dicarboxy group in the molecule, and a difunctional epoxy compound (ΠΙ) (the above compound having a carboxyl group (Π) and a difunctional epoxy At least one of the compounds (III) is a compound having no aromatic ring, and is characterized in that: the epoxy group having an unsaturated group at the side chain and having an epoxy group at the same time and having an epoxy group at the terminal end is not The reaction of the saturated monocarboxylic acid (c) is carried out by reacting a hydroxyl group with a polybasic acid anhydride (d). 2. The active energy ray-curable resin according to claim 1, wherein the compound (II) having at least a dicarboxy group in the molecule is selected from 1,2-cyclohexene dicarboxylic acid having no aromatic ring, At least one of a group of tetrahydrofurfuric acid, hexahydrophthalic acid, hexahydroisodecanoic acid, and hexahydrotereic acid. 3. The active energy ray-curable resin according to claim 1 or 2, wherein the The functional epoxy compound (III) is a hydrogenated difunctional epoxy compound. A photocurable thermosetting resin composition comprising: (A) polyanthracene anhydride (a) and a compound (b) having at least one unsaturated double bond and one alcoholic hydroxyl group in one molecule Reaction product (I), a polyaddition reaction product of a compound (II) having at least a dicarboxy group and a polyfunctional epoxy compound (III) in a molecule of -49 - (2) 1325877 (wherein the above compound having a carboxyl group (II) And at least one of the polyfunctional epoxy compound (III) is a compound having no aromatic ring), an epoxy group having an unsaturated group at its side chain and having an epoxy group at the same time, and an epoxy group having a terminal epoxy group An unsaturated monocarboxylic acid (C) reaction, an active energy ray-curable resin obtained by reacting a hydroxyl group in a molecule with a polybasic acid anhydride (d), (B) a photopolymerization initiator, (C) a diluent, and (D) An aqueous alkali solution of a cyclic ether compound having two or more epoxy groups and/or an oxygen group in one molecule can be visualized. 5. The active energy ray-curable resin composition of claim 4, wherein the compound having at least a dicarboxy group in the molecule of the active energy ray-curable resin (A) is selected from the group consisting of no aromatic ring At least one of 1,2-cyclohexene dicarboxylic acid, tetrahydrofurfuric acid, hexahydrononanoic acid, hexahydroisodecanoic acid, and hexahydropyridinic acid. 6. The active energy ray-curable resin composition according to claim 4 or 5, wherein the difunctional epoxy compound (ΠΙ) of the active energy ray-curable resin (A) is a hydrogenated difunctional ring Oxygen compound. 7. The photocurable/thermosetting resin composition of any one of claims 4 to 6 which further contains (E) a curing catalyst. 8. The photocuring property according to any one of claims 4 to 7, wherein the thermosetting tree composition further contains an active energy ray-curable resin other than the active energy ray-curable resin (A) (F) ). -50- (3) 1325877 9. A cured product characterized by being photocurable and thermosetting resin composition according to any one of claims 4 to 8, which is irradiated with active energy rays and/or Or heat hardened. A printed circuit board characterized by forming an interlayer insulating layer and/or a solder resist layer by a photocurable thermosetting resin composition according to any one of claims 4 to 8; to make. -51 -