JP2010280876A - Photocurable resin composition, photocurable drip-proof insulative paint, electric and electronic components prepared using the same and method of manufacturing the component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable drip-proof insulative paint, etc. for mounted circuit boards, which are curable in a short time and exhibit moisture resistance sufficient for mounting. <P>SOLUTION: There are provided a photocurable resin composition containing (A) an acrylic polymer, (B) a polyfunctional epoxy compound, (C) an oxetane ring-containing compound and (D) a photopolymerization initiator, a photocurable drip-proof insulative paint for mounted circuit boards containing the resin composition, electric or electronic components for which the paint is used, and a method of manufacturing the components. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition comprising an acrylic polymer, a polyfunctional epoxy compound, an oxetane ring-containing compound, and a photopolymerization initiator, a photocurable drip-proof insulating coating for a mounting circuit board comprising the same, and The present invention relates to an electric component or an electronic component used, and a manufacturing method thereof.

  2. Description of the Related Art Conventionally, an electronic component is manufactured in which a wiring diagram is printed with a predetermined metal on a substrate such as glass epoxy or ceramic, and an IC, a capacitor, a resistor, and the like are mounted at the predetermined position. In recent years, in order to obtain an electronic component having high reliability even when used in a high-temperature and high-humidity environment, a moisture-proof insulating coat has been applied. This is because by applying the coating, the insulation resistance is maintained while being protected from moisture and condensed water even under high temperature and high humidity.

  As such moisture-proof insulating coating agents for forming surface insulation films for electronic parts, acrylic resins, urethane resins, epoxy resins, etc. are generally used as paint raw materials for aromatic hydrocarbons, ketones, esters, etc. The thing of the form of a solvent-type coating material melt | dissolved in the organic solvent used is used. And the coating agent is apply | coated to the surface of an electronic component etc. by the spray method, the immersion method, the brush coating method, etc., and it heat-drys, and forms a moisture-proof insulation coat film.

  On the other hand, in the form of solvent-based paint, the environmental load becomes a problem, so instead of the organic solvent in the solvent-based moisture-proof insulating paint, water-based moisture-proof using water with no environmental load as the solvent (dispersion medium) For the purpose of providing an insulating coating agent, Patent Document 1 discloses an aqueous moisture-proof insulating coating agent containing water and a coating component dispersed in water. The coating component includes an acrylic resin and a petroleum-based coating agent. An aqueous moisture-proof insulating coating agent characterized by containing a wax and / or polyethylene wax has been proposed, and Patent Document 2 discloses an aqueous moisture-proof insulating coating agent containing an acrylic resin. The acrylic resin is a copolymer having a structural unit derived from (A) styrene and a structural unit derived from (B) (meth) acrylic acid alkyl ester, and (A) component and (B) Mixing ratio of the minute mass ratio (A) :( B) = 1: 1~2: Aqueous moisture-proof insulation coating agent has been proposed is 1.

However, these water-proof and moisture-proof insulating coating agents need to be processed over time and temperature in order to volatilize water as a solvent in the drying process, resulting in increased costs and CO ₂ emissions due to longer processing time. There is a problem that increases.

Further, Patent Document 3 discloses a photocurable moisture-proof insulating paint that can be processed for a short time, has excellent moisture resistance, adhesion to a substrate, and resin strength (hardness), and is moisture-proof insulated by applying and curing the same. For the purpose of providing an electronic component and a method for producing the same, (A) acryloxy polybutadiene or acryloxy hydrogenated polybutadiene, (B) bisphenol A-based (meth) acrylate, and (C) a general formula CH ₂ ═C (R ¹ ) —COO—R ² (wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group or an alkenyl group having 5 to 20 carbon atoms), and (D ) A photocurable moisture-proof insulating paint containing a photopolymerization initiator, wherein the content of the component (B) is 1 to 30 weights with respect to the total amount of the component (A) and the component (B). % Light characterized by Resistance moisture-proof insulation coating material has been proposed.

  However, the photocurable moisture-proof insulating coating does not have sufficient moisture resistance for in-vehicle use, and further improvement is required.

JP 2007-154004 A JP 2007-154005 A JP 2008-303362 A

  The present invention has been made in view of such problems of the prior art, and is a photocurable resin composition that can be cured for a short time and exhibits sufficient moisture resistance for in-vehicle use, and such photocurability. A photocurable drip-proof insulating coating for mounting circuit boards containing a resin composition, an electric or electronic component such as an electronic circuit board that has been drip-proof insulated using such a photocurable drip-proof insulating coating, and its An object of the present invention is to provide a method for manufacturing such an electrical component or electronic component.

  The photocurable resin composition according to the first aspect of the present invention includes, as described in claim 1, (A) an acrylic polymer, (B) a polyfunctional epoxy compound, (C) a compound having an oxetane ring, And (D) a photopolymerization initiator.

  In the first invention of this application, it is possible to provide a photocurable resin composition that can be used as a photocurable moisture-proof insulating coating for electronic circuit boards.

  As one preferable form of the photocurable resin composition which is the first aspect, the content of the component (C) is the component (A), the component (B), the component (C) and the component (C). D) The photocurable resin composition characterized by being 10-70 weight% with respect to the total amount of a component is mentioned (refer Claim 2).

  As another preferable embodiment of the photocurable resin composition according to the first aspect, the component (A) is at least one acrylic selected from the group consisting of a copolymer of an acrylic monomer and a vinyl acetate monomer. The photocurable resin composition which is a polymer is mentioned (refer Claim 3).

  As another preferred embodiment of the photocurable resin composition according to the first aspect, the component (B) contains two or more epoxy groups in one molecule, an aromatic epoxy resin, an alicyclic epoxy The photocurable resin composition which is at least 1 type of polyfunctional epoxy compound selected from the group which consists of resin and an aliphatic epoxy resin is mentioned (refer Claim 4).

  As another preferred embodiment of the photocurable resin composition according to the first aspect, the component (C) is at least one oxetane ring selected from the group consisting of compounds containing one or two oxetane rings. The photocurable resin composition which is a compound which has is mentioned (refer Claim 5).

  As another preferred embodiment of the photocurable resin composition according to the first aspect, the component (D) is at least one photopolymerization selected from the group consisting of onium salts that release a Lewis acid by photoreaction. The photocurable resin composition which is an initiator is mentioned (refer Claim 6).

  The photocurable drip-proof insulating coating for a mounting circuit board according to the second aspect of the present invention contains the photocurable resin composition according to the first aspect as described in claim 7. It is a feature.

  In the photocurable drip-proof insulating paint for mounting circuit boards according to the second aspect, it is possible to sufficiently maintain the insulation resistance even in high-temperature and high-humidity in an in-vehicle electronic circuit board.

  The electrical component or electronic component according to the third aspect of the present invention is insulated using the photocurable drip-proof insulating paint for mounting circuit boards according to the second aspect as described in claim 8. It is characterized by this.

  The electric component or electronic component according to the third aspect can have sufficient moisture resistance for in-vehicle use.

  According to a fourth aspect of the present invention, there is provided a method for manufacturing an electrical component or an electronic component, wherein the photocurable drip-proof insulating paint for a mounted circuit board according to the second aspect is electrically It is applied to at least a part of the surface of the electronic component, and then the applied photocurable drip-proof insulating coating for mounting circuit board is cured to insulate the electric / electronic component. .

  In the electric component or electronic component manufacturing method according to the fourth aspect, a vehicle-mounted electronic circuit board can be obtained.

  As the acrylic polymer as the component (A) in the present invention, a copolymer of an acrylic monomer and a vinyl acetate monomer is preferable, and a copolymer of an acrylic monomer, a vinyl acetate monomer, and a functional group-containing monomer is particularly preferable. .

  Although it does not specifically limit as an acryl-type monomer, For example, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate , Glycidyl methacrylate, 2-hydroxyethyl methacrylate and the like. Among these, one or more selected from ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferable.

  Further, the functional group-containing monomer is not particularly limited, but for example, methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, Examples include acrylamide, methylol acrylamide, glycidyl methacrylate, maleic anhydride and the like.

  Among such acrylic polymers, more preferred are polyethylhexyl acrylate, polyglycidyl methacrylate and the like.

  Moreover, as a content rate of the acryl-type polymer in a photocurable resin composition, it is 5-5 with respect to the total amount of the said (A) component, the said (B) component, the said (C) component, and the said (D) component. It is preferably 94% by weight, more preferably 7 to 50% by weight, and particularly preferably 10 to 20% by weight. If the content of the acrylic polymer is lower than 5% by weight, a blended system is found and does not disperse uniformly, and if it exceeds 94% by weight, it is difficult to maintain insulation resistance at high temperature and high humidity.

  The polyfunctional epoxy compound which is component (B) in the present invention is a compound containing two or more epoxy groups in one molecule, and preferred examples thereof include aromatic epoxy resins and alicyclic epoxy resins. And aliphatic epoxy resins.

  Preferred as the aromatic epoxy resin is a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, for example, bisphenol A or bisphenol F or an alkylene oxide adduct thereof, epichlorohydrin, The glycidyl ether and epoxy novolac resin produced by the reaction of

  Further, preferred as the alicyclic epoxy resin is a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, or a cyclohexene or cyclopentene ring-containing compound, which is appropriately oxidized with hydrogen peroxide, peracid or the like. And cyclopentene oxide-containing compounds obtained by epoxidizing with an agent. Representative examples of the alicyclic epoxy resin include 3,4-epoxycyclohexenecarboxylate, bisphenol-A glycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′- Epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene Epoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, etc. It is done.

  Further preferred as aliphatic epoxy resins are polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, and the like. Typical examples are 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycol. One or more alkylene oxides are added to aliphatic polyhydric alcohols such as glycidyl ether, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol and glycerin. Polyglycidyl ethers of polyether polyols obtained by the addition, include diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, monoglycidyl ether of higher aliphatic alcohol, phenol, cresol, butylphenol or polyether alcohol monoglycidyl ether obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acid, epoxidized soybean oil, epoxy butyl stearate Octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene and the like.

  Among such polyfunctional epoxy compounds, more preferable are 3,4-epoxycyclohexene carboxylate, bisphenol-A glycidyl ether, and the like.

  Moreover, as a content rate of the polyfunctional epoxy compound in a photocurable resin composition, it is 1 with respect to the total amount of the said (A) component, the said (B) component, the said (C) component, and the said (D) component. -94 wt% is preferable, 15-65 wt% is more preferable, and 20-50 wt% is particularly preferable. When the content ratio of the polyfunctional epoxy compound is lower than 1% by weight, it is not preferable because it is difficult to maintain the insulation resistance at high temperature and high humidity, and when it exceeds 94% by weight, the blended system is squeezed and uniform dispersion is not preferable.

で表されるオキセタン環を少なくとも１つ有する化合物であればいずれでも使用することができる。例えばオキセタン環を１ないし１５含有する化合物が挙げられ、好ましくは１ないし１０含有する化合物、特に好ましくは１または２個含有する化合物である。 The compound having an oxetane ring as the component (C) in the present invention is represented by the following general formula (1).

Any compound having at least one oxetane ring represented by the formula can be used. Examples thereof include compounds containing 1 to 15 oxetane rings, preferably 1 to 10 compounds, particularly preferably 1 or 2 compounds.

で示される化合物等が挙げられる。一般式（２）において、Ｚ、Ｒ¹、Ｒ²は下記の原子又は置換基を意味する。Ｚは酸素原子または硫黄原子を示す。Ｒ¹は水素原子、フッ素原子、メチル基、エチル基、プロピル基、ブチル基等の炭素原子数１〜６個のアルキル基、トリフルオロメチル基、パーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基等の炭素原子数１〜６個のフルオロアルキル基、フェニル基、ナフチル基等の炭素数６〜１８のアリール基、フリル基またはチエニル基である。Ｒ²は、水素原子、メチル基、エチル基、プロピル基、ブチル基等の炭素原子数１〜６個のアルキル基、１−プロペニル基、２−プロペニル基、２−メチル−１−プロペニル基、２−メチル−２−プロペニル基、１−ブテニル基、２−ブテニル基、３−ブテニル基等の炭素原子数２〜６個のアルケニル基；ベンジル基、フルオロベンジル基、メトシキベンジル基、フェネチル基、スチリル基、シンナミル基、エトキシベンジル基等の置換または非置換の炭素原子数７〜１８のアラルキル基；フェノキシメチル基、フェノキシエチル基等のアリーロキシアルキル基等のその他の芳香環を有する基；エチルカルボニル基、プロピルカルボニル基、ブチルカルボニル基等の炭素原子数２〜６個のアルキルカルボニル基；エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基等の炭素原子数２〜６個のアルコキシカルボニル基；エチルカルバモイル基、プロピルカルバモイル基、ブチルカルバモイル基、ペンチルカルバモイル基等の炭素原子数２〜６個のＮ−アルキルカルバモイル基が挙げられる。又本願発明の効果を阻害しない範囲で上記以外の置換基を用いてもよい。 As the compound having one oxetane ring, any compound having one oxetane ring can be used, but the following compounds can be preferably used. For example, the following general formula (2)

And the like. In the general formula ^{(2), Z, R 1} , R 2 denotes an atom or a substituent described below. Z represents an oxygen atom or a sulfur atom. R ¹ is a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, butyl group or other alkyl group having 1 to 6 carbon atoms, trifluoromethyl group, perfluoromethyl group, perfluoroethyl group, perfluoro A fluoroalkyl group having 1 to 6 carbon atoms such as a propyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group, a furyl group or a thienyl group; R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, Alkenyl groups having 2 to 6 carbon atoms such as 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group; benzyl group, fluorobenzyl group, methoxybenzyl group, phenethyl group A substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms such as a styryl group, a cinnamyl group, and an ethoxybenzyl group; a group having other aromatic rings such as an aryloxyalkyl group such as a phenoxymethyl group and a phenoxyethyl group; An alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group; An alkoxycarbonyl group having 2 to 6 carbon atoms such as a xoxycarbonyl group and a butoxycarbonyl group; an N-alkylcarbamoyl group having 2 to 6 carbon atoms such as an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group and a pentylcarbamoyl group Groups. Moreover, you may use substituents other than the above in the range which does not inhibit the effect of this invention.

  As more specific examples of the compound having one oxetane ring, Aron Oxetane OXT-101, Aron Oxetane OXT-211, Aron Oxetane OXT-212, Aron Oxetane OXT-213 (the above are manufactured by Toa Gosei Co., Ltd.), 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3 -Oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isovol Luoxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3- Oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylethyl (3-ethyl-3-oxetanylmethyl) ) Ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl- -Oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3- Oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, penta Examples include bromophenyl (3-ethyl-3-oxetanylmethyl) ether and bornyl (3-ethyl-3-oxetanylmethyl) ether.

  Examples of the compound having two oxetane rings include compounds represented by the following general formula (3) and the following general formula (8).

ここで、Ｒ¹は一般式（２）と同様に水素原子、フッ素原子、メチル基、エチル基、プロピル基、ブチル基等の炭素原子数１〜６個のアルキル基、トリフルオロメチル基、パーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基等の炭素原子数１〜６個のフルオロアルキル基、フェニル基、ナフチル基等の炭素数６〜１８のアリール基、フリル基またはチエニル基である。一般式（３）中のＲ¹は互いに同じでも異なっていてもよい。Ｒ³は、エチレン基、プロピレン基、ブチレン基等の線状あるいは分岐状の炭素原子数１〜２０のアルキレン基、ポリ（エチレンオキシ）基、ポリ（プロピレンオキシ）基等の線状あるいは分枝状の炭素原子数１〜１２０のポリ（アルキレンオキシ）基、プロペニレン基、メチルプロペニレン基、ブテニレン基等の線状あるいは分枝状の不飽和炭素水素基、カルボニル基、カルボニル基を含むアルキレン基、分子鎖の途中にカルバモイル基を含むアルキレン基である。また、Ｒ³は、下記一般式（４）〜（６）で示される基から選択される多価の基でもよい。 That is, the compound represented by the general formula (3) is as follows.

Here, R ¹ is a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, butyl group or other alkyl group having 1 to 6 carbon atoms such as general formula (2), trifluoromethyl group, A fluoroalkyl group having 1 to 6 carbon atoms such as a fluoromethyl group, a perfluoroethyl group or a perfluoropropyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group or a naphthyl group, a furyl group or a thienyl group; . R ¹ in the general formula (3) may be the same as or different from each other. R ³ is a linear or branched linear or branched alkylene group having 1 to 20 carbon atoms such as an ethylene group, a propylene group or a butylene group, a poly (ethyleneoxy) group or a poly (propyleneoxy) group. Linear or branched unsaturated carbon hydrogen groups such as poly (alkyleneoxy) groups having 1 to 120 carbon atoms, propenylene groups, methylpropenylene groups, butenylene groups, carbonyl groups, and carbonyl groups An alkylene group containing a carbamoyl group in the middle of the molecular chain. R ³ may be a polyvalent group selected from the groups represented by the following general formulas (4) to (6).

一般式（４）において、Ｒ⁴は、水素原子、メチル基、エチル基、プロピル基、ブチル基等の炭素原子数１〜４個のアルキル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素原子数１〜４個のアルコキシ基、塩素原子、臭素原子等のハロゲン原子、ニトロ基、シアノ基、メルカプト基、低級アルキルカルボキシル基、カルボキシル基、または、カルバモイル基であり、Ｘは１〜４の整数である。 General formula (4) is the following substituents.

In the general formula (4), R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. An alkoxy group having 1 to 4 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group, and X is 1 to 1 It is an integer of 4.

一般式（５）において、Ｒ⁵は、酸素原子、硫黄原子、メチレン基、−ＮＨ−、−ＳＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−または−Ｃ（ＣＨ₃）₂−である。 General formula (5) is the following substituents.

In the general formula (5), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group, —NH—, —SO—, —SO ₂ —, —C (CF ₃ ) ₂ — or —C (CH ₃ ) ₂ —. It is.

一般式（６）において、Ｒ⁶は、メチル基、エチル基、プロピル基、ブチル基等の炭素原子数６〜１８のアリール基であり、ｙは、０〜２００の整数である。Ｒ⁷はメチル基、エチル基、プロピル基、ブチル基等の炭素原子数６〜１８のアリール基である。又Ｒ⁷は、下記一般式（７）で示される基でもよい。

一般式（７）において、Ｒ⁸は、メチル基、エチル基、プロピル基、ブチル基等の炭素原子数６〜１８のアリール基である。Ｚは、０〜１００の整数である。 General formula (6) is the following substituents.

In the general formula (6), R ⁶ is a methyl group, an ethyl group, a propyl group, an aryl group having 6 to 18 carbon atoms such as butyl group, y is an integer of 0 to 200. R ⁷ is an aryl group having 6 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. R ⁷ may be a group represented by the following general formula (7).

In General formula (7), R < ⁸ > is C6-C18 aryl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group. Z is an integer of 0-100.

一般式（８）において、 Ｒ¹は一般式（２）と同様に水素原子、フッ素原子、メチル基、エチル基、プロピル基、ブチル基等の炭素原子数１〜６個のアルキル基、トリフルオロメチル基、パーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基等の炭素原子数１〜６個のフルオロアルキル基、フェニル基、ナフチル基等の炭素数６〜１８のアリール基、フリル基またはチエニル基である。一般式（２）中のＲ¹は互いに同じでも異なっていてもよい。 The compound represented by the general formula (8) is as follows.

In the general formula (8), R ¹ is a hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, butyl group or other alkyl group having 1 to 6 carbon atoms as in the general formula (2), trifluoro C1-C6 fluoroalkyl group such as methyl group, perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, aryl group having 6-18 carbon atoms such as phenyl group, naphthyl group, furyl group, or Thienyl group. R ¹ in the general formula (2) may be the same as or different from each other.

および下記式（１０）が挙げられる。

As a more specific compound having two oxetane rings, the following formula (9)

And the following formula (10).

  Furthermore, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl -3-oxetanylmethoxy) methyl] ethane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis ( 3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylenebis (3-Ethyl-3-oxetanylmethyl) ether, 1,4-bis [( -Ethyl-3-oxetanylmethoxy) methyl] butane, 1,6-bis [(3-ethyl-3-oxetanylmethoxy) methyl] hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Among these compounds having an oxetane ring, more preferable examples include Aron Oxetane OXT-211 and Aron Oxetane OXT-212. Aron Oxetane OXT-211 is particularly preferable.

  Moreover, as a content rate of the compound which has an oxetane ring in a photocurable resin composition, with respect to the total amount of the said (A) component, the said (B) component, the said (C) component, and the said (D) component, It is preferably 5 to 75% by weight, more preferably 10 to 70% by weight, and particularly preferably 30 to 60% by weight. When the content ratio of the compound having an oxetane ring is less than 5% by weight, it is not preferable because the insulation resistance of the electronic circuit board at high temperature and high humidity cannot be maintained, and when it exceeds 75% by weight, the mixture is not preferably uniformly dispersed.

The photopolymerization initiator as the component (D) in the present invention is not particularly limited as long as it is a compound that initiates polymerization of the compound having an oxetane ring as the component (C) by light, and any of them can be used. As a preferred example of the photopolymerization initiator, the general formula (11)
_{^{[R 12 a R 13 b R}} 14 c R 15 d W] m + [MX n + m] m- (11)
(Wherein the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N, and R ¹² , R ¹³ , R ¹⁴ and R15 are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. M is a halogenated complex [MX _{n + m} ] or a metal or metalloid constituting the central atom of, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, X is a halogen atom such as F, Cl, Br, etc., m is the net charge of the halide complex ion, and n is the valence of M. The onium salt which has can be mentioned. This onium salt is a compound that photoreacts and releases a Lewis acid.

Specific examples of the onium ion in the general formula (11) include isopropyl-methyldiphenyliodonium, diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (Dodecylphenyl) iodonium, tricumyliodonium, triphenylsulfonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di ( 4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η ⁵ -2,4- (cyclopentagenyl) [1,2,3,4,5,6-η- (methylethyl) benzene ]-Iron (1 +) And the like. Specific examples of anions in the general formula (23) include tetrafluoroborate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, hexachloroantimonate and the like. These photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  Of such photopolymerization initiators, isopropyl-methyldiphenyliodonium and the like are particularly preferable.

  Moreover, as a content rate of the photoinitiator in a photocurable resin composition, it is 0 with respect to the total amount of said (A) component, said (B) component, said (C) component, and said (D) component. 0.1 to 5% by weight is preferable, and 0.5 to 2% by weight is particularly preferable. When the content of the photopolymerization initiator is lower than 0.1% by weight, it is not preferable because a cured product cannot be obtained due to insufficient curing, and when it exceeds 5% by weight, the material cost becomes high and is not practical. .

  Also, in the method for producing an electrical component or electronic component according to the present invention, the above-mentioned photocurable drip-proof insulating coating for mounting circuit board is applied to at least a part of the surface of the electric / electronic component, and then the applied mounting circuit board is applied. This includes curing the photo-curable drip-proof insulating paint for use in insulating the electrical and electronic parts. The method for applying the photocurable drip-proof insulating coating for mounting circuit boards there may be a commonly used method, and specific examples include brush coating, dip coating, and spray coating. Moreover, as a method of hardening the apply | coated photocurable drip-proof insulation coating material for mounting circuit boards, the method used normally may be used, Specifically, ultraviolet curing, heat curing, etc. are mentioned.

  Examples of the present invention will be described below more specifically with reference to examples of the present invention. However, the present invention is not limited to these examples. In addition, unless otherwise indicated, the quantity of each component showing the composition in the following Examples and Comparative Examples is expressed by “parts by weight”.

  “Humidity resistance” in Examples and the like is an insulation resistance value [Ω] measured using a JIS type II comb substrate in a humidity environment of a temperature of 80 ° C. and a relative humidity of 95% at an applied voltage of 20V. It is shown by.

  “Compatibility” in Examples and the like means a state in which a mixture in which each composition is mixed is uniformly dispersed, and is visually determined. In some cases, aggregates are not confirmed after the mixture is prepared. O: The case where an aggregate was confirmed after the mixture was created is represented by x.

Examples 1-5, Comparative Example 1
Polyethylhexyl acrylate (manufactured by Sanyo Chemical Industries, Ltd.) (Examples 1-5, Comparative Example 1) or polyglycidyl methacrylate (manufactured by NOF Corporation) (Examples 1-5, Comparative Example 1) as an acrylic polymer As a polyfunctional epoxy compound, 3,4-epoxycyclohexenecarboxylate (manufactured by Junsei Chemical Co., Ltd.) (Examples 1 to 5, Comparative Example 1) or bisphenol-A glycidyl ether (manufactured by Japan Epoxy Resin Co., Ltd.) (implemented) Examples 1-5, Comparative Example 1), Aron Oxetane (produced by Toagosei Co., Ltd.) (Examples 1-5, Comparative Example 1) as a compound having an oxetane ring, and isopropyl-methyldiphenyliodonium (Tokyo) as a photopolymerization initiator (Made by Kasei Kogyo Co., Ltd.) (Examples 1 to 5 and Comparative Example 1), with the compositions shown in Table 1 and planetary stirring By mixing was used to prepare a photocurable resin composition.

  Using each photocurable resin composition sample obtained, their compatibility and insulation resistance [Ω] were determined. The obtained results are shown in Table 1.

As shown in Table 1, any of Examples 1 to 5 containing a compound having an oxetane ring as component (C) as compared with Comparative Example 1 not containing a compound having an oxetane ring as component (C) Also, a high insulation resistance value [Ω] of 10 ⁸ to 10 ⁹ was obtained, and good moisture resistance, that is, moisture-proof insulation was obtained. In addition, regarding compatibility, only Example 5 containing the largest amount of a compound having an oxetane ring as 80 wt% was a result in which compatibility was not obtained.

Claims (9)

  A photocurable resin composition comprising (A) an acrylic polymer, (B) a polyfunctional epoxy compound, (C) a compound having an oxetane ring, and (D) a photopolymerization initiator.   The content of the component (C) is 10 to 70% by weight based on the total amount of the component (A), the component (B), the component (C) and the component (D). The photocurable resin composition according to claim 1.   The photocurable resin composition according to claim 1 or 2, wherein the component (A) is at least one acrylic polymer selected from the group consisting of a copolymer of an acrylic monomer and a vinyl acetate monomer.   At least one polyfunctional epoxy compound selected from the group consisting of an aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin, wherein the component (B) contains two or more epoxy groups in one molecule The photocurable resin composition according to claim 1 or 2, wherein   The photocurable resin composition according to claim 1 or 2, wherein the component (C) is a compound having at least one oxetane ring selected from the group consisting of compounds containing one or two oxetane rings. .   The photocurable resin composition according to claim 1 or 2, wherein the component (D) is at least one photopolymerization initiator selected from the group consisting of onium salts that undergo a photoreaction to release a Lewis acid.   A photocurable drip-proof insulating coating for a mounting circuit board, comprising the photocurable resin composition according to any one of claims 1 to 6.   An electrical component or an electronic component, wherein the electrical component or the electronic component is insulated using the photocurable drip-proof insulating paint for mounting circuit boards according to claim 7.   The photocurable drip-proof insulating paint for mounting circuit boards according to claim 7 is applied to at least a part of an electric / electronic component, and then the applied photocurable drip-proof insulating paint for mounted circuit boards is cured. An electrical component or an electronic component manufacturing method, characterized in that the electrical / electronic component is insulated.