JP2013100550A - Curable composition including epoxy group-containing ester compound, method for producing the composition, and the epoxy group-containing ester compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition including an epoxy group-containing ester compound, which has high reactivity and is used as various crosslinking agents and a reactive diluent, and whose cured product is excellent in electrical characteristics, dimensional stability, heat resistance, weather resistance, chemical resistance, and mechanical characteristics and is useful as various moldings or optical materials, and a method for producing the same.SOLUTION: The curable composition includes an epoxy group-containing ester compound represented by structural formula. In formula, Rrepresents an organic residue derived from (poly)carbonate polyol having a structural unit derived from an alkane diol having a 9C or more branched structure and/or cyclic structure; Rs each independently represents H or CH; Rand Reach independently represents OR group or OH group, wherein R is an organic residue; m is an integer of 1-4; n is an integer of 0-3; and l is an integer of 0-3.

Description

  The present invention relates to a curable composition containing an epoxy group-containing ester compound, a method for producing the composition, and an epoxy group-containing ester compound. More specifically, in addition to being highly reactive and used as various crosslinking agents and reactive diluents, the cured product itself has excellent electrical properties, dimensional stability, heat resistance, weather resistance, chemical resistance, and mechanical properties. The present invention relates to a curable composition containing an epoxy group-containing ester compound useful as a molded article or an optical material, a method for producing the composition, and an epoxy group-containing ester compound.

  Conventionally, epoxy compounds having a glycidyl group have been widely used as useful cross-linking agents such as electrical insulating materials, adhesives, paints, and matrix resins for composite materials. Among them, glycidyl ester compounds having a glycidyl group via an ester bond are known to have high curing reactivity. For example, glycidyl ester compounds such as glycidyl methacrylate and triglycidyl trimellitic acid are used in the above fields. Many are used.

  In recent years, alicyclic epoxy group-containing compounds have been proposed for the purpose of improving the water resistance, weather resistance, or heat resistance of epoxy compounds having a glycidyl group via an ester bond. Alicyclic epoxy group-containing compounds are used as UV-curing coating materials and transparent sealing materials because they have smaller shrinkage in curing than glycidyl ether-type epoxy compounds and are excellent in precision molding and heat resistance. .

  On the other hand, the alicyclic epoxy group-containing compound is required to be improved in mechanical properties because its cured product is hard and easily cracked. In addition, with the recent increase in the integration density of IC chips, the distance between wirings of a printed wiring board tends to be shortened, and the electrical insulation performance of the resin is not sufficient for application thereto.

  As a typical example of an alicyclic epoxy group-containing compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate can be mentioned. In order to improve the mechanical properties of this compound, a patent is given. Document 1 proposes a compound having the following structural formula. However, a cured product of a compound having the following structure does not have sufficient electrical insulation performance.

また、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートの機械物性を向上させるために、特許文献２に下記一般式（ＩＩＩ）で表される化合物が提案されている。しかし、この特許文献２には電気絶縁特性に関しては、具体的には全く開示されていない。

Moreover, in order to improve the mechanical properties of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Patent Document 2 proposes a compound represented by the following general formula (III). However, this patent document 2 does not disclose any specific electrical insulation characteristics.

（式中、Ｒ⁷は、ジオール化合物ＨＯ−Ｒ⁷−ＯＨの残基を示す。ｑは０〜５の整数であり分布を有する。）
なお、本明細書に記載の「脂環式エポキシ基」とは、例えば、シクロヘキセンオキサイドのような脂環基内部に存在するエポキシ基を意味する。

(In the formula, R ⁷ represents a residue of the diol compound HO—R ⁷ —OH. Q is an integer of 0 to 5 and has a distribution.)
In addition, the “alicyclic epoxy group” described in the present specification means an epoxy group existing inside the alicyclic group such as cyclohexene oxide.

JP 2006-52187 A JP 2007-161652 A

  An object of the present invention is to provide a curable composition containing a novel epoxy group-containing compound capable of obtaining a cured product particularly excellent in electrical insulation properties, and a method for producing the same.

  As a result of repeated studies to solve the above problems, the present inventors have found that a cured product obtained by curing a composition containing a novel epoxy group-containing ester compound having a specific structure has particularly good electrical insulating properties. It has been found that it is excellent, and the present invention has been completed.

That is, the present invention includes the following embodiments.
[1] A curable composition containing an epoxy group-containing ester compound represented by the following general formula (I).

（式中、Ｒ¹は、炭素数９以上の分岐構造及び／又は環状構造を有する飽和炭化水素鎖を含み、かつ炭素数の総計が１２以上である多価アルコールから誘導される有機残基を表す。Ｒ²は、それぞれ独立にＨ又はＣＨ₃を表す。Ｒ³、Ｒ⁴はそれぞれ独立にＯＲ基又はＯＨ基を表す。ここでＲは有機残基である。ｍは１〜４の整数、ｎは０〜３の整数、ｌは０〜３の整数を表す。）
[２]前記一般式（Ｉ）中のＲ¹が、トリシクロ［５．２．１．０^2,6］デカンジメタノールから誘導される有機残基であることを特徴とする[１]に記載の硬化性組成物。

(In the formula, R ¹ represents an organic residue derived from a polyhydric alcohol containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total carbon number of 12 or more. R ² represents each independently H or CH ₃ , R ³ and R ⁴ each independently represents an OR group or an OH group, where R is an organic residue, and m is an integer of 1 to 4. N represents an integer of 0 to 3, and l represents an integer of 0 to 3.)
[2] according to R ¹ in the general formula (I) is, tricyclo [5.2.1.0 ^{2, 6],} characterized in that an organic residue derived from decanedimethanol [1] Curable composition.

[3] The curable composition according to [1], wherein R ¹ in the general formula (I) is an organic residue derived from dimer diol.
[4] R ¹ in the general formula (I) is an organic residue derived from a (poly) carbonate polyol having a structural unit derived from an alkanediol having a branched structure and / or a cyclic structure having 9 or more carbon atoms. The curable composition according to [1], which is characterized in that it exists.

[5] The curable composition according to any one of [1] to [4], further comprising either a curing agent or a polymerization initiator.
[6] An alicyclic epoxy group-containing carboxylic acid ester represented by the following general formula (II), a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and a total number of carbon atoms: [1], which comprises a step of producing an epoxy group-containing ester compound represented by the above general formula (I) by reacting a polyhydric alcohol of 12 or more with a transesterification catalyst. The manufacturing method of curable composition of description.

（式中、Ｒ⁵はＨ又はＣＨ₃を表し、Ｒ⁶は炭素数１〜４のアルキル基又は炭素数３〜４のアルケニル基を表す。）
[７]前記炭素数９以上の分岐構造及び／又は環状構造を有する飽和炭化水素鎖を含みかつ炭素数の総計が１２以上である多価アルコールが、トリシクロ［５．２．１．０^2,6］デカンジメタノールであることを特徴とする[６]に記載の硬化性組成物の製造方法。

(In the formula, R ⁵ represents H or CH ₃ , and R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)
[7] The polyhydric alcohol containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total carbon number of 12 or more is tricyclo [5.2.1.0 ^{2, 6} ] The method for producing a curable composition as described in [6], which is decanedimethanol.

  [8] The polyhydric alcohol containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total carbon number of 12 or more is a dimer diol [6] ] The manufacturing method of the curable composition as described in any one of.

  [9] The polyhydric alcohol containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total carbon number of 12 or more is a branched structure and / or cyclic structure having 9 or more carbon atoms. The method for producing a curable composition according to [6], which is a (poly) carbonate polyol having a structural unit derived from an alkanediol having a structure.

  [10] The transesterification catalyst is at least one compound selected from the group consisting of dialkyltin oxides, tetraalkyl titanates and metal acetylacetonate complexes. [6] to [9] The manufacturing method of the curable composition of any one.

[11] The method for producing a curable composition according to any one of [6] to [9], wherein the transesterification catalyst is dibutyltin oxide or dioctyltin oxide.
[12] The transesterification catalyst includes an alicyclic epoxy group-containing carboxylic acid ester and a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and the total number of carbon atoms is 12 or more. The method for producing a curable composition according to any one of [6] to [11], wherein the content is 0.01 to 3.0% by mass relative to the total amount of the polyhydric alcohol.

  [13] An epoxy group-containing ester compound represented by the following formula (1).

[１４]下記式（２）で表されるエポキシ基含有エステル化合物。

[14] An epoxy group-containing ester compound represented by the following formula (2).

[１５]下記式（３）で表されるエポキシ基含有エステル化合物。

[15] An epoxy group-containing ester compound represented by the following formula (3).

（式中、ｏは０以上の整数、ｐは０以上の整数を表し、かつｏ＋ｐは１以上の自然数である。）

(In the formula, o represents an integer of 0 or more, p represents an integer of 0 or more, and o + p is a natural number of 1 or more.)

The curable composition containing the epoxy group-containing ester compound of the present invention includes a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and a total number of carbon atoms of 12 or more. It contains a specific compound having an organic residue derived from and gives a cured product having excellent electrical insulation properties. In the present invention, the alicyclic epoxy group-containing carboxylic acid ester, a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and the total number of carbon atoms is 12 or more. By carrying out a transesterification reaction with alcohol and reacting while distilling off the generated alcohol component, it is possible to efficiently produce a composition containing the target epoxy group-containing ester compound of the present invention, thereby reducing the industrial cost. It has become possible to provide a manufacturing method.

It is a ¹ H-NMR spectrum of the product obtained in Example of Synthesis Example A-1. It is a FTIR spectrum of the product obtained in Example of Synthesis Example A-1. It is a < ¹ > H-NMR spectrum of the product obtained in Example of Synthesis Example A-2. It is a FTIR spectrum of the product obtained in the implementation synthesis example A-2. It is a < ¹ > H-NMR spectrum of the product obtained in Example of Synthesis Example A-3. It is a FTIR spectrum of the product obtained in the implementation synthesis example A-3.

Hereinafter, the present invention will be specifically described.
The curable composition of this invention contains the epoxy group containing ester compound represented by the following general formula (I).

式（Ｉ）中、Ｒ¹は、炭素数９以上の分岐構造及び／又は環状構造を有する飽和炭化水素鎖を含み、かつ炭素数の総計が１２以上である多価アルコールから誘導される有機残基を表す。Ｒ²は、それぞれ独立にＨ又はＣＨ₃を表す。Ｒ³、Ｒ⁴はそれぞれ独立にＯＲ基又はＯＨ基を表す。ここでＲは有機残基である。ｍは１〜４の整数、ｎは０〜３の整数、ｌは０〜３の整数を表す。

In the formula (I), R ¹ represents an organic residue derived from a polyhydric alcohol containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total carbon number of 12 or more. Represents a group. R ² independently represents H or CH ₃ . R ³ and R ⁴ each independently represents an OR group or an OH group. Here, R is an organic residue. m represents an integer of 1 to 4, n represents an integer of 0 to 3, and l represents an integer of 0 to 3.

As used herein, “including a saturated hydrocarbon chain having a branched structure and / or cyclic structure having 9 or more carbon atoms” means that if the hydrocarbon chain having 9 or more carbon atoms is saturated, it may be branched or cyclic structure Or may have both a branched structure and a cyclic structure. That is, it means that it has a chain structure in which nine or more carbon atoms are bonded in a branched and / or cyclic manner by a saturated bond without intervening atoms other than carbon atoms. Here, when R ¹ is an organic residue derived from a polyhydric alcohol consisting of only a linear saturated hydrocarbon chain having 9 or more carbon atoms and a total of 12 or more carbon atoms, In many cases, it has crystallinity, which is not preferable for handling. In the present invention, the branched and / or cyclic bonded chain structure has a branched chain and / or cyclic bonded chain structure having 9 or more carbon atoms in the molecule, and has carbon atoms. It is obtained by using a polyhydric alcohol having a total number of 12 or more as a raw material.

Hereinafter, by way of example, an organic residue (R) containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total carbon number of 12 or more (R ¹ ) is explained.

  Examples of the organic residue derived from a polyhydric alcohol and having a branched saturated hydrocarbon chain having 9 or more carbon atoms include those represented by the following structural formulas (5) to (7).

また、多価アルコールから誘導される、炭素数９以上の環状構造の飽和炭化水素鎖を有する有機残基としては、以下のような構造式（８）〜（１１）のものを挙げることもできる。なお、分子構造上、炭素数９以上の環状構造の飽和炭化水素鎖を有する有機残基は、炭素数９以上の分岐状の飽和炭化水素鎖を有する有機残基に含まれることもある。

In addition, examples of the organic residue having a saturated hydrocarbon chain having a cyclic structure of 9 or more carbon atoms derived from a polyhydric alcohol include the following structural formulas (8) to (11). . Note that an organic residue having a saturated hydrocarbon chain having a cyclic structure having 9 or more carbon atoms may be included in an organic residue having a branched saturated hydrocarbon chain having 9 or more carbon atoms.

上記構造式（５）〜（１１）のうち、上記構造式（８）、（１０）、（１１）は、「炭素数の総計が１２以上」であるという条件も満たしている。従って、これらは一般式（Ｉ）のＲ¹に含まれる。これに対して、上記構造式（５）〜（７）、（９）は「炭素数の総計が１２以上」であるという条件を満たさない。従って、これらは、Ｒ¹には含まれない。

Among the structural formulas (5) to (11), the structural formulas (8), (10), and (11) also satisfy the condition that “the total number of carbon atoms is 12 or more”. Accordingly, these are included in R ¹ of the general formula (I). On the other hand, the structural formulas (5) to (7) and (9) do not satisfy the condition that “the total number of carbon atoms is 12 or more”. Therefore, these are not included in R ¹ .

However, for example, if the structural unit of the structural formula (5) is an organic residue represented by the following structural formula (12) in which two molecules are bonded via a carbonate bond, “branched saturated carbonization having 9 or more carbon atoms” The condition “organic residue derived from a polyhydric alcohol containing a hydrogen chain and having a total carbon number of 12 or more” is satisfied. Therefore, structural formula (12) is included in R ¹ .

なお、Ｒ¹中に、多価アルコールから誘導される炭素数９以上の分岐構造及び／又は環状構造を有する飽和炭化水素鎖を有する場合、カーボネート結合を介して、多価アルコールから誘導される炭素数９以上の直鎖状の飽和炭化水素鎖を含んでいてもよい。この場合、上記の構造式（１２）と同様に、炭素数の総計が１２以上の要件も満たす。

In addition, when R ¹ has a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms derived from a polyhydric alcohol, the carbon derived from the polyhydric alcohol via a carbonate bond. A linear saturated hydrocarbon chain of several 9 or more may be included. In this case, similarly to the above structural formula (12), the total number of carbons satisfies the requirement of 12 or more.

R ^{1 includes} an organic residue derived from a polyhydric alcohol having a hydrocarbon chain having less than 9 carbon atoms, a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and the total number of carbon atoms Is an organic residue derived from a polyhydric alcohol having 11 or less, the electrical insulation property of the cured product obtained by curing the compound is a branched structure and / or a cyclic structure having 9 or more carbon atoms. It tends to be lower than the electrical insulating properties of a cured product obtained using an organic residue derived from a polyhydric alcohol having a saturated hydrocarbon chain and having a total carbon number of 12 or more, It is not preferable.

Preferred structures of R ¹ include organic residues derived from tricyclo [5.2.1.0 ^2,6 ] decandimethanol, organic residues derived from dimer diol, branched structures having 9 or more carbon atoms, and Examples thereof include organic residues derived from a (poly) carbonate polyol having a structural unit derived from an alkanediol having a cyclic structure.

  The “dimer diol” described in the present specification is mainly a diol having about 36 carbon atoms in which dimer acid and / or its lower alcohol ester is hydrogenated in the presence of a catalyst and the carboxylic acid portion of dimer acid is alcohol. Ingredients. Hydrogenated dimer diol in which the carbon-carbon double bond derived from dimer acid is also hydrogenated is particularly preferred. As a commercial item, PRIPOL2033 etc. (made by a Unikema company) and Sovermol908 (made by a Cognis company) can be mentioned, for example. The “dimer acid” referred to here is an acid obtained by an intermolecular polymerization reaction of an unsaturated fatty acid, which is obtained by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms, and has about 36 carbon atoms. The dibasic acid is the main component. Examples of commercially available products include PRIPOL 1006, 1009, 1015, 1025, etc. (manufactured by Unikema) and EMPOL1062 (manufactured by Cognis).

  The expression “(poly) carbonate” in the (poly) carbonate polyol described in the present specification means that the molecule has one or more carbonate bonds. Therefore, “(poly) carbonate polyol” described in the present specification means a compound having one or more carbonate bonds and two or more alcoholic hydroxyl groups in the molecule. Examples thereof include (poly) carbonate diol having two hydroxyl groups in one molecule, (poly) carbonate triol having three or more hydroxyl groups in one molecule, and (poly) carbonate tetraol.

  (Poly) carbonate polyol is dimerized or polymerized from a monomer through a carbonate bond. A polyhydric alcohol can be used as the monomer. As a method for producing a carbonate bond using a polyhydric alcohol, for example, it can be synthesized by transesterification of a polyhydric alcohol and a carbonate in the presence of a catalyst.

  Monomers that produce (poly) carbonate polyols include aliphatic polyhydric alcohols having 9 or more carbon atoms and branched hydrocarbons as a skeleton, and aliphatic polyvalent alcohols having 9 or more carbon atoms and a cyclic structure. Alcohol or an aliphatic polyhydric alcohol having both a branched structure and a cyclic structure can be used. Among them, the aliphatic polyhydric alcohol having a branched hydrocarbon as a skeleton tends to lower the viscosity of the (poly) carbonate polyol to be produced.

The average molecular weight of the (poly) carbonate polyol is preferably 3000 or less. A curable composition containing an epoxy group-containing ester compound produced using a (poly) carbonate polyol having an average molecular weight of 3000 or less can be cured to provide a cured product having sufficient chemical resistance. The average number of hydroxyl groups in the (poly) carbonate polyol compound is 2 or more per molecule, and preferably 2 or more and 4 or less. However, the viscosity of the epoxy group-containing ester compound is decreased and the epoxy group-containing ester compound is used. From the viewpoint of reducing the variation in viscosity, it is particularly preferable to use a diol component as a main component as a monomer for producing the (poly) carbonate polyol. Specific examples of the diol component include 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol or 1,2-tetradecanediol, and tricyclo [5.2.1.0. ^2,6 ] decanedimethanol and the like.

  The (poly) carbonate diol may be a (poly) carbonate diol (copolymerized (poly) carbonate diol) having a plurality of types of alkylene groups in its skeleton, and the use of the copolymerized (poly) carbonate diol is an epoxy. In many cases, it is advantageous from the viewpoint of preventing crystallization of the group-containing ester compound.

  In addition, if it is a range which does not impair the electrical insulation characteristic of hardened | cured material, polyhydric alcohol other than the polyhydric alcohol which has a saturated hydrocarbon chain which has a C9 or more branched structure and / or cyclic structure, and Structural formula (13) A polyhydric alcohol having a linear hydrocarbon chain having 9 or more carbon atoms as shown in (14) can be used as one component of the copolymerized (poly) carbonate polyol. Examples of the latter include a case where o in the structural formula (3) is not 0.

一般式（Ｉ）中、Ｒ²は、それぞれ独立にＨ又はＣＨ₃を表す。ここで言う「それぞれ独立に」とは、例えば、一般式（Ｉ）中、ｍ＝３の場合には、１分子中に３個のＲ²が存在することになり、その３個のＲ²が、それぞれ独立にＨ又はＣＨ₃であることを意味する。即ち、３個のＲ²のすべてがＨであっても、３個のＲ²のすべてがＣＨ₃であっても、或いは３個のＲ²の内２個がＨで１個がＣＨ₃であっても、２個がＣＨ₃で１個がＨであっても、いっこうに差し支えないことを意味する。同様に、ｍ＝ｌ＝１の場合、１分子中に２個のＲ²が存在することになり、その２個のＲ²が、それぞれ独立にＨ又はＣＨ₃であることを意味する。即ち、２個のＲ²のすべてがＨであっても、２個のＲ²のすべてがＣＨ₃であっても、一方のＲ²がＨであり他方のＲ²がＣＨ₃であってもいっこうに差し支えないことを意味する。

In the general formula (I), R ² represents H or CH ₃ independently. Here, “independently” means, for example, in the general formula (I), when m = 3, three R ² exist in one molecule, and the three R ² Each independently represents H or CH ₃ . That is, all three R ² are H, all three R ² are CH ₃ , or two of the three R ² are H and one is CH ₃ . Even if two are CH ₃ and one is H, it means that there is no problem. Similarly, when m = 1, it means that ^two R ² exist in one molecule, and the two R ² are each independently H or CH ₃ . That is, even if all ^two R ² are H, all two R ² are CH ₃ , one R ² is H and the other R ² is CH ₃ It means that there is no problem.

In general formula (I), R ³ and R ⁴ each represents an OR group (R is an organic residue) or an OH group. R ³ and R ⁴ may have the same structure or different structures. Further, when l is 2 or 3, which means that the plurality of R ³ and R ⁴ in the molecule is present, a plurality of R ³ and R ⁴ may be the same structure, different It may be a structure.

  In general formula (I), m is an integer of 1-4, More preferably, it is an integer of 2-4. When m = 0, the compound does not contain an epoxy group in the molecule, and is not included in the epoxy group-containing ester compound of the present invention. Moreover, when it is an integer of m> = 5, since the hardened | cured material becomes hard too much, it is unpreferable. When only the compound of m = 1 is used, the cured product becomes a linear polymer, which is not preferable because resistance to chemicals such as solvent resistance is lowered. However, when used in combination with a compound in which m is an integer of 2 to 4, the cured product can have sufficient chemical resistance.

  In general formula (I), l and n each represent an integer of 0 to 3. When l is an integer of 4 or more, the epoxy group content is relatively small, which is not preferable. Further, when n is an integer of 4 or more, the water resistance of the compound tends to decrease, which is not preferable.

  Examples of the compound represented by the general formula (I) include the compounds represented by the structural formulas (1) to (3) and the compounds represented by the following structural formulas (15) and (16).

次に、本発明のエポキシ基含有エステル化合物を含む硬化性組成物の製造方法について説明する。

Next, the manufacturing method of the curable composition containing the epoxy group containing ester compound of this invention is demonstrated.

  The curable composition containing the epoxy group-containing ester compound of the general formula (I) includes an alicyclic epoxy group-containing carboxylic acid ester represented by the following general formula (II), a branched structure having 9 or more carbon atoms, and / or Alternatively, a corresponding epoxy group-containing ester compound can be produced by reacting with a polyhydric alcohol containing a saturated hydrocarbon chain having a cyclic structure and having a total number of carbon atoms of 12 or more using a transesterification catalyst. .

（式中、Ｒ⁵はＨ又はＣＨ₃を表し、Ｒ⁶は炭素数１〜４のアルキル基又は炭素数３〜４のアルケニル基を表す。）
まず、本発明のエポキシ基含有エステル化合物を含む硬化性組成物の原料成分である上記一般式（ＩＩ）で表される脂環式エポキシ基含有カルボン酸エステルについて説明する。式中、Ｒ⁵はＨ又はＣＨ₃を表す。また、式中、Ｒ⁶は炭素数１〜４までのアルキル基又は炭素数１〜４までのアルケニル基を表す。具体的には、メチル基、エチル基、ｎ―プロピル基、イソピロピル基、ｎ−ブチル基、イソブチル基、アリル基、メタリル基、３−ブテニル基等を挙げることができる。これらの中で、エステル交換反応の進行のし易さ及び発生するアルコールの留去のし易さを考慮すると、好ましいものとしては、メチル基、エチル基、ｎ―プロピル基、アリル基、メタリル基であり、さらに好ましくは、アリル基、メタリル基である。なお、このような脂環式エポキシ基含有カルボン酸エステルとしては、３，４−エポキシシクロヘキサン−１−カルボン酸アリルなどが挙げられる。

(In the formula, R ⁵ represents H or CH ₃ , and R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)
First, the alicyclic epoxy group-containing carboxylic acid ester represented by the general formula (II), which is a raw material component of the curable composition containing the epoxy group-containing ester compound of the present invention, will be described. In the formula, R ⁵ represents H or CH ₃ . In the formula, R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an allyl group, a methallyl group, and a 3-butenyl group. Among these, considering the ease of progress of the transesterification reaction and the ease of distilling off the generated alcohol, preferred are methyl group, ethyl group, n-propyl group, allyl group, methallyl group. And more preferably an allyl group or a methallyl group. Examples of the alicyclic epoxy group-containing carboxylic acid ester include allyl 3,4-epoxycyclohexane-1-carboxylate.

  Next, the raw material component of the curable composition containing the epoxy group-containing ester compound of the present invention is “including a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and a total of 12 carbon atoms. The above-mentioned “polyhydric alcohol” will be described.

“Polyhydric alcohol containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total carbon number of 12 or more, which is a raw material component of the method for producing an epoxy group-containing ester compound of the present invention” "Saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms" is as described above, and a branched structure having 9 or more carbon atoms as R ¹ in the general formula (I) and / or A polyhydric alcohol containing a saturated hydrocarbon chain having a cyclic structure and having a total carbon number of 12 or more can be used as a raw material.

Preferable polyhydric alcohol that can be used as a raw material in the present invention has tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, dimer diol, a branched structure having 9 or more carbon atoms, and / or a cyclic structure. Examples thereof include (poly) carbonate polyol having a structural unit derived from alkanediol.

Next, the transesterification catalyst used as an essential component in the manufacturing method of the curable composition containing the epoxy group containing ester compound of this invention is demonstrated.
As the transesterification catalyst, basically any catalyst can be used as long as it activates an ester group to cause a reaction with an alcohol. For example, alkali metals, alkaline earth metals and alkali metals, alkaline earth metal oxides, weak alkali metal and alkaline earth metal salts, alkali metal and alkaline earth metal alcoholates, alkali metal and alkaline earth metal water Oxides, and oxides of Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co, and Sn, and hydroxylation of Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co, and Sn Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn inorganic acid salts, Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn alkoxides, Hf, Organic acid salts of Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn, acetylacetonates of Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn Organic complex, dibutyltin oxide as, dioctyltin oxide, organotin compounds such as dibutyltin dichloride, dimethyl aniline, 1,4-diazabicyclo [2.2.2] tertiary amine such as octane or the like.

  Among these, dialkyltin compounds such as dibutyltin oxide, dioctyltin oxide, dibutyltin dichloride, tetraalkyl titanates such as tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, manganese acetylacetonate, zirconium acetylacetonate, hafnium It is preferable to use a metal acetylacetonate complex such as acetylacetonate.

  Among these, particularly preferred are dialkyltin compounds such as dibutyltin oxide, dioctyltin oxide and dibutyltin dichloride, metal acetylacetonate complexes such as manganese acetylacetonate, zirconium acetylacetonate and hafnium acetylacetonate. Most preferred are dibutyltin oxide and dioctyltin oxide.

  The form of the reaction includes an alicyclic epoxy group-containing carboxylic acid ester represented by the general formula (II) and a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a carbon number. A method is employed in which polyhydric alcohol having a total of 12 or more is heated in the presence of a transesterification catalyst. The reaction temperature varies depending on the type of transesterification catalyst to be used, but is selected from the range of 30 to 200 ° C., preferably 50 to 160 ° C., in an inert gas atmosphere at normal pressure or under pressure, or as necessary. It is desirable to react under reduced pressure. Furthermore, in order to carry out the reaction efficiently, it is better to distill the generated alcohol component out of the reaction system quickly.

The amount of the alicyclic epoxy group-containing carboxylic acid ester represented by the general formula (II) is used to complete the reaction (that is, saturated carbonization having a branched structure and / or a cyclic structure having 9 or more carbon atoms as a raw material). Saturated carbonization having a branched structure and / or a cyclic structure having 9 or more carbon atoms as a raw material in order to convert most of the hydroxyl groups of the polyhydric alcohol having a hydrogen chain and having 12 or more carbon atoms into esters. A theoretical amount or more is required for a polyhydric alcohol containing a hydrogen chain and having a total carbon number of 12 or more. However, in consideration of reaction rate, equilibrium, etc., it is better to use an excess molar amount. However, even if the alicyclic epoxy group-containing carboxylic acid ester is used in an excessive amount, an effect commensurate with the excess amount is not exhibited, and this is not economically preferable.

  In addition, the amount of the alicyclic epoxy group-containing carboxylic acid ester used includes the case where the reaction does not need to be completed (that is, the saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms as a raw material). In addition, when a part of the hydroxyl group of the polyhydric alcohol having a total carbon number of 12 or more may be left unreacted), it is saturated having a branched structure and / or a cyclic structure as a raw material. Even less than the theoretical amount can be used for polyhydric alcohols containing hydrocarbon chains and having a total carbon number of 12 or more.

  Therefore, the use amount of the alicyclic epoxy group-containing carboxylic acid ester usually includes a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms as a raw material, and the total number of carbon atoms is 12 or more. It is 0.8-5.0 times mole with respect to the theoretical amount of polyhydric alcohol, More preferably, it is 0.9-4.0 times mole. As a charging method in that case, it may be charged at the beginning of the reaction or may be added sequentially during the reaction.

  The transesterification catalyst is used in an amount of carboxylic acid ester containing an alicyclic epoxy group and a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and the total number of carbon atoms is 12 or more. It is 0.01-3 mass% with respect to the total amount of a polyhydric alcohol, Preferably it is about 0.02-0.4 mass%. When the amount is less than 0.01% by mass, the reaction rate is slow. When the amount is more than 3% by mass, not only an effect corresponding to the amount is obtained but also the coloration becomes severe, and the yield is increased due to side reactions. May fall. Further, depending on the type of transesterification catalyst to be used, excessive use has a problem that it takes a lot of time and labor to separate from the transesterification catalyst.

  The method for isolating the epoxy group-containing ester compound represented by the general formula (I) produced in this reaction system varies depending on the type of catalyst used. For example, when dibutyltin dioxide is used, In the case where the epoxy group-containing ester compound represented by the above general formula (I) is a distillable compound after the alcohol component and unreacted alicyclic epoxy group-containing carboxylic acid ester generated by distillation are distilled off under reduced pressure A purified product that can be used as a product can be obtained simply by performing distillation purification. In addition, in the case where the epoxy group-containing ester compound represented by the general formula (1) thus produced is a compound that cannot be distilled, it can be purified using means such as washing with water. In this way, compounds such as the structural formulas (1) to (3), (15), (16) can be isolated. In the method for producing a curable composition of the present invention, since the amount of the transesterification catalyst used is very small, the alcohol component generated by the reaction and the unreacted alicyclic epoxy group-containing carboxylic acid ester are distilled off under reduced pressure. You can also use it as it is. In addition, the reaction product usually contains a plurality of types of epoxy group-containing ester compounds represented by the above general formula (I), but the cured product obtained from the composition containing these mixtures also has good electrical insulation properties. Is expressed.

  In order to obtain a cured product from the curable composition containing the epoxy group-containing ester compound represented by the general formula (I) of the present invention, either a curing agent or a polymerization initiator for curing the composition is included. These will be described below.

First, the case where a curing agent is included will be described.
The curing agent that can be contained in the curable composition of the present invention is not particularly limited as long as it is a compound that can cure the epoxy group-containing ester compound represented by the general formula (I). For example, phenol compounds such as phenol resin, amine compounds such as diamine and polyamine, acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, polyvalent carboxyl group-containing compounds such as trimellitic acid, etc. One of these compounds may be used alone, or two or more thereof may be used in combination.

  There is no restriction | limiting in particular as a phenolic compound which can be used as a hardening | curing agent. For example, a phenol compound having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent may be used, and 2 in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol, and the like. Compounds having one phenolic hydroxyl group, phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthol such as α-naphthol, β-naphthol, dihydroxynaphthalene Novolak type phenolic resin obtained by condensation or cocondensation of aldehydes with formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. in the presence of an acidic catalyst Phenol and aralkyl resins synthesized from alcohols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, aralkyl-type phenol resins such as naphthol aralkyl resins, paraxylylene and / or metaxylylene-modified phenol resins, melamine-modified phenol resins Terpene-modified phenol resins, dicyclopentadiene-type phenol resins, dicyclopentadiene-type naphthol resins, cyclopentadiene-modified phenol resins, polycyclic aromatic ring-modified, synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene Phenolic resins, biphenyl type phenolic resins, triphenylmethane type phenolic resins, phenolic resins obtained by copolymerizing two or more of these, and the like are used alone It may also be used in combination of two or more.

  Among the above-mentioned phenol compounds, from the viewpoint of reflow crack resistance, there are aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, benzaldehyde type and aralkyl type copolymer type phenol resins, and novolak type phenol resins. Aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, and benzaldehyde type and aralkyl type copolymer type phenol resins are more preferable. These preferred phenol resins may be used alone or in combination of two or more. However, in order to exert their performance, the above preferred phenol resins are used with respect to the total amount of the phenol resin. Is preferably 30% by mass or more, and more preferably 50% by mass or more.

  When only a phenol compound is used as the curing agent, the amount used is such that the ratio of the total number of phenolic hydroxyl groups to the total number of epoxy groups in the curable composition is in the range of 0.7 to 1.5. More preferably, it is in the range of 0.8 to 1.2. If the ratio of the total number of phenolic hydroxyl groups to the total number of epoxy groups in the composition is less than 0.7, the crosslinking density is undesirably low. On the other hand, when the ratio is larger than 1.5, the electrical insulation properties and water resistance of a cured product obtained by curing the composition tend to deteriorate, which is not preferable.

  It does not specifically limit as an acid anhydride which can be used as a hardening | curing agent. For example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride Products, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride and the like. Among these, acid anhydrides which are liquid at 25 ° C., for example, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride, trialkyltetrahydro Examples thereof include phthalic anhydride, dodecenyl succinic anhydride, 2,4-diethylglutaric anhydride, etc. Among them, alicyclic acid anhydride is preferable, and methylhexahydrophthalic anhydride and hydrogenated methylnadic acid anhydride are particularly preferable. These acid anhydrides may be used alone or as a mixture thereof, and may be, for example, a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride. Further, it may be a mixture of acid anhydrides obtained by dissolving a solid acid anhydride in a liquid acid anhydride and becoming liquid at 25 ° C.

  When only an acid anhydride is used as the curing agent, the amount used is such that the ratio of the total number of acid anhydride groups to the total number of epoxy groups in the composition is within the range of 0.7 to 1.5. Is preferable, and more preferably within the range of 0.8 to 1.2. If the total number of acid anhydride groups relative to the total number of epoxy groups in the composition is less than 0.7, the crosslinking density is undesirably low. On the other hand, when the ratio is larger than 1.5, the electrical insulation properties and water resistance of a cured product obtained by curing the composition tend to deteriorate, which is not preferable.

  The amine compound that can be used as the curing agent is not particularly limited as long as it is a compound having a primary and secondary amino group. For example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, metaxylylenediamine, diaminodiphenylmethane, phenylenediamine, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, norbornane Polyamines such as diamines, polyamide polyamine compounds obtained by reacting the polyamines with carboxylic acids such as monomer acids and dimer acids, Mannich type curing agents which are polycondensates of the polyamines, phenols and formaldehyde, the polyamines An epoxy adduct type curing agent in which an epoxy resin or the like is added to the above. These amine compounds may be used alone or as a mixture thereof.

  When only an amine compound is used as a curing agent, the amount used thereof is within the range represented by the following formula from the viewpoint of water resistance and heat resistance of a cured product obtained by curing the composition. preferable.

0.7 ≦ (total number of secondary amino groups in the composition + total number of primary amino groups in the composition × 2) / total number of epoxy groups in the composition ≦ 1.5
Examples of the polyvalent carboxyl group-containing compound that can be used as a curing agent include trimelotic acid, pyromellitic acid, succinic acid, adipic acid, glutaric acid, and a carboxyl group-containing polyurethane described in JP2007-154134A. it can. Dicarboxylic acids such as succinic acid, adipic acid and glutaric acid are preferably used in combination with a trifunctional or higher polycarboxylic acid rather than used alone from the viewpoint of heat resistance of the cured product.

  When only the polycarboxylic acid is used as the curing agent, the amount used is such that the ratio of the total number of carboxyl groups to the total number of epoxy groups in the curable composition of the present invention is in the range of 0.7 to 1.5. Preferably, it exists in the range of 0.8-1.2. When the ratio of the total number of carboxyl groups to the total number of epoxy groups in the composition is less than 0.7, the crosslinking density is undesirably low. On the other hand, when the ratio is larger than 1.5, the electrical insulation properties and water resistance of a cured product obtained by curing the composition tend to deteriorate, which is not preferable.

  A phenol compound, an acid anhydride, an amine compound, and a polycarboxylic acid that can be used as a curing agent may be mixed and used. From the viewpoint that the electrical insulation properties of the cured product obtained by curing the composition of the present invention are sufficiently exhibited, acid anhydrides or polyvalent carboxyl group-containing compounds are preferred among the curing agents.

A curing accelerator can be used in the curable composition of the present invention as necessary. In particular, when the curing agent to be used is selected from phenol compounds, acid anhydrides and polycarboxylic acids, it is preferable to use a curing accelerator in combination. The curing accelerator that can be used in combination is not limited as long as it is a compound that accelerates the reaction between the epoxy group-containing compound and the curing agent. For example, melamine, acetoguanamine, benzoguanamine, 2,4-diamino-6-methacryloyl Oxyethyl-s-triazine, 2,4-methacryloyloxyethyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine and isocyanuric acid addition Triazine compounds such as imidazole, 2-imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2 -Phenyl-4-methylimidazole, 1-cyanoe Ru-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1- (cyanoethylaminoethyl ) -2-methylimidazole, N- [2- (2-methyl-1-imidazolyl) ethyl] urea, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1- Cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-tria Gin, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N′— Bis (2-methyl-1-imidazolylethyl) adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-methylimidazole isocyanuric acid adduct,
2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-methyl-4-formyl Imidazole, 2-ethyl-4-methyl-5-formylimidazole, 2-phenyl-4-methylformylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1- (2-hydroxyethyl ) Imidazole, vinylimidazole, 1-methylimidazole, 1-allylimidazole, 2-ethylimidazole, 2-butylimidazole, 2-butyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2- a] benzimidazole, 1-benzyl-2-phenylimidazo Hydrobromide, imidazole compounds such as 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5. 4.0] Cycloamidine compounds such as diazabicycloalkenes such as undecene-7 and derivatives thereof, tertiary amino groups such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol Containing compounds, triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris ( Trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc. Organic phosphine compounds, dicyandiazide and the like.

  These curing accelerators may be used alone or in combination of two or more. Among these curing accelerators, preferred are triazine compounds, imidazole compounds and tertiary amino group-containing compounds.

  The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect can be achieved. However, from the viewpoints of the curability of the composition of the present invention and the electrical insulating properties and water resistance of the cured product obtained by curing the composition of the present invention, a total of 100 epoxy group-containing compounds in the composition of the present invention. It is preferable to mix | blend within the range of 0.1-10 mass parts with respect to a mass part, More preferably, it is 1-7.0 mass parts. When the blending amount is less than 0.1 parts by mass, it is difficult to cure in a short time, and when it exceeds 10 parts by mass, the electrical insulating properties and water resistance of the cured product obtained by curing the composition are deteriorated. There is.

  Moreover, in the curable composition of this invention, other epoxy group containing compounds other than the epoxy group containing ester compound represented by general formula (I) can be used together. Examples of the epoxy group-containing compound other than the epoxy group-containing ester compound represented by the general formula (I) include phenol novolac type epoxy resins, orthocresol novolak type epoxy resins, phenol, cresol, xylenol, resorcin, and catechol. Acid catalysts for phenols such as bisphenol A and bisphenol F and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde Novolak type epoxy resin obtained by epoxidizing novolak resin obtained by condensation or cocondensation below, bisphenol A, bisphenol F, bisphenol S, alkyl substitution Or diglycidyl ethers such as unsubstituted biphenols and stilbene phenols (bisphenol type epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins), glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol, phthalic acid Glycidyl ester type epoxy resin of carboxylic acids such as isophthalic acid and tetrahydrophthalic acid, glycidyl type or methyl glycidyl type epoxy resin such as aniline, isocyanuric acid or the like substituted with active hydrogen bonded to nitrogen atom with glycidyl group, Vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- Of alicyclic epoxy resins such as 3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin, terpene modified phenolic resin Glycidyl ether, glycidyl ether of dicyclopentadiene modified phenolic resin, glycidyl ether of cyclopentadiene modified phenolic resin, glycidyl ether of polycyclic aromatic ring modified phenolic resin, glycidyl ether of naphthalene ring-containing phenolic resin, halogenated phenol novolac type epoxy resin, Hydroquinone type epoxy resin, trimethylolpropane type epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid, diphenyl Tan epoxy resins, phenol aralkyl resins, aralkyl type phenol resin epoxy compound, such as naphthol aralkyl resin, a sulfur atom-containing epoxy resins and the like.

  The curable composition of the present invention may contain various additives as necessary. Typical additives include, for example, an antioxidant for preventing oxidative deterioration due to heat during curing and making the cured product less colored, and an ultraviolet absorber for further improving the light resistance of the cured product. It is done.

  As the antioxidant, an antioxidant such as phenol, sulfur, and phosphorus can be used, and the blending ratio thereof is 10 mass with respect to 100 mass parts of the total amount of the epoxy group-containing compound in the composition of the present invention. Part or less.

  As the ultraviolet absorber, ultraviolet absorbers such as benzophenone, benzotriazole, hindered amine, and salicylic acid can be used, and the blending ratio thereof is 100 parts by mass with respect to the total amount of the epoxy group-containing compound in the composition of the present invention. The amount is preferably 10 parts by mass or less.

  As other additives, for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, metal hydroxides such as aluminum hydroxide, kaolin, mica, quartz powder, Powdered fillers such as graphite, molybdenum disulfide and glass beads; Colorants or pigments such as titanium dioxide, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, organic dyes; antimony trioxide, bromine compounds, phosphorus compounds, etc. It is also possible to add a flame retardant or the like. These blending ratios are usually 100 parts by mass or less for the powdery filler, and 30 parts by mass for the colorant, pigment and flame retardant, respectively, with respect to 100 parts by mass of the total amount of the epoxy group-containing ester compound in the composition of the present invention. Part or less. Furthermore, a leveling agent, a coupling agent, an ion adsorbent, etc. can be used together as needed.

Next, the case where a polymerization initiator is included will be described.
The polymerization initiator that can be contained in the curable composition of the present invention is not particularly limited as long as a cured product can be obtained from the epoxy group-containing ester compound represented by the general formula (I). Absent. Similar to a compound having a normal alicyclic epoxy group, a cured product can be obtained by performing cationic polymerization using a cationic polymerization initiator.

  The cationic polymerization initiator that can be used is not particularly limited as long as it is a compound that initiates ring-opening polymerization of an epoxy group. Cationic polymerization initiators are broadly classified into thermal cationic polymerization initiators that generate active species by heat and photocationic polymerization initiators that generate active species when irradiated with light, and are represented by general formula (I). As a cationic polymerization initiator for cationically polymerizing a composition containing an epoxy group-containing ester compound, either a thermal cationic polymerization initiator or a photocationic polymerization initiator may be used, or a combination thereof may be used. .

The cationic photopolymerization initiator is a compound that initiates cationic polymerization of an epoxy group upon irradiation with ultraviolet rays. For example, the cation moiety is sulfonium, iodonium, diazonium, ammonium, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe cation, and the anion moiety is BF ₄ ⁻ , PF _An onium salt composed of ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups). Specifically, sulfonium salts include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenyl). Sulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) ) Phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) pheny Rusulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- ( 2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate and the like, iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (Pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) Borate, 4-methylphenyl-4- (1-methyl) Chill) iodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyl iodonium tetrafluoroborate,
Examples of diazonium salts such as 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium Tetrakis (pentafluorophenyl) borate and the like include ammonium salts such as 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoro Borate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl)- -Cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salts such as (pentafluorophenyl) borate include (2,4-cyclopentadien-1-yl) [(1 -Methylethyl) benzene] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, 2,4- Cyclopentadien-1-yl) [(1-methylethyl Benzene] -Fe (II) tetrafluoroborate, 2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate, and the like.

  Commercially available products of these cationic photopolymerization initiators include, for example, UVI-6990, UVI-6974 (manufactured by Dow Chemical), Optmer SP-150, Optomer SP-170 (manufactured by ADEKA), FC-508, FC -512 (manufactured by 3M), Irgacure 261 (manufactured by Ciba Specialty Chemicals), RHODROSIL PHOTOINITITOR 2074 (manufactured by Rhodia), CD-1012 (manufactured by SARTOMER), PCI-019, PCI-021 (Nippon Kayaku ( Co., Ltd.), CPI-100P, CPI-100A (manufactured by San Apro Co., Ltd.), TEPBI-S (manufactured by Nippon Shokubai Co., Ltd.), Sun-Aid SI-60L, SI-80L and SI-100L (Sanshin) Chemical Industry Co., Ltd.), UVE-1014 and UVE-1016 General Electric (General Electric) Co., Ltd.), KI-85 (Degussa (Degussa) Co., Ltd.), and the like are available.

  Cationic or protonic acid catalyst such as triflic acid salt, boron trifluoride ether complex compound, boron trifluoride, etc. as thermal cationic polymerization initiator, various oniums such as ammonium salt, phosphonium salt and sulfonium salt A salt can be used.

  Examples of triflate salts include diethylammonium triflate, triethylammonium triflate, diisopropylammonium triflate, ethyl diisopropylammonium triflate available from 3M as FC-520 (many of which are 1980 by RR Alm Modern Coatings, published October 2010).

  Examples of the ammonium salt include those represented by the following general formula (IV).

式中、Ｒ⁹〜Ｒ¹²は、それぞれ独立に、炭素数１〜２０のアルキル基、炭素数５〜１２のシクロアルキル基、炭素数３〜１２のアルケニル基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、又は炭素数１〜２０のアルコキシ基であり、さらに、置換基を有していてもよい。また、Ｒ⁹〜Ｒ¹²のうちの２個が互いに結合して、Ｎ、Ｐ、Ｏ、又はＳ原子を含む複素環を形成していてもよい。Ｘ^-は対イオンを表し、ＢＦ₄ ^-、ＡｓＦ₆ ^-、ＳｂＦ₆ ^-、ＳｂＣｌ₆ ^-、（Ｃ₆Ｆ₅）₄Ｂ^-、ＳｂＦ₅（ＯＨ）^-、ＨＳＯ₄ ^-、ｐ−ＣＨ₃Ｃ₆Ｈ₄ＳＯ₃ ^-、ＨＣＯ₃ ^-、Ｈ₂ＰＯ₄ ^-、ＣＨ₃ＣＯ₂ ^-、ハロゲンイオン（Ｃｌ^-、Ｂｒ^-、Ｉ^-等）などから選ばれる。

In the formula, R ^{9 to} R ¹² are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and may further have a substituent. Also, two of R ^{9 to} R ¹² may be bonded to each other to form a heterocyclic ring containing N, P, O, or S atoms. X ⁻ represents a counter ion, BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , SbF ₅ (OH) ⁻ , HSO ₄ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , HCO ₃ ⁻ , H ₂ PO ₄ ⁻ , CH ₃ CO ₂ ⁻ , halogen ions (Cl ⁻ , Br ⁻ , I ^{− and the} like) and the like.

  Specifically, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, N, N-dimethyl-N-benzylanily Nium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyltrifluoromethanesulfonate, N , N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl-N- (4-methoxybenzyl) ) Such as preparative Luigi hexafluoroantimonate are mentioned as preferred.

  Examples of the phosphonium salt include those represented by the following general formula (V).

式中、Ｒ¹³〜Ｒ¹⁶は、それぞれ独立に、炭素数１〜２０のアルキル基、炭素数５〜１２のシクロアルキル基、炭素数３〜１２のアルケニル基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、又は炭素数１〜２０のアルコキシ基であり、さらに、置換基を有していてもよい。また、Ｒ¹³〜Ｒ¹⁶のうちの２個が互いに結合して、Ｎ、Ｐ、Ｏ、又はＳ原子を含む複素環を形成していてもよい。Ｙ^-は対イオンを表し、ＢＦ₄ ^-、ＡｓＦ₆ ^-、ＳｂＦ₆ ^-、ＳｂＣｌ₆ ^-、（Ｃ₆Ｆ₅）₄Ｂ^-、ＳｂＦ₅（ＯＨ）^-、ＨＳＯ₄ ^-、ｐ−ＣＨ₃Ｃ₆Ｈ₄ＳＯ₃ ^-、ＨＣＯ₃ ^-、Ｈ₂ＰＯ₄ ^-、ＣＨ₃ＣＯ₂ ^-、ハロゲンイオン（Ｃｌ^-、Ｂｒ^-、Ｉ^-等）などから選ばれる。

In the formula, R ^{13 to} R ¹⁶ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and may further have a substituent. Two of R ^{13 to} R ¹⁶ may be bonded to each other to form a heterocyclic ring containing an N, P, O, or S atom. Y ⁻ represents a counter ion, BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , SbF ₅ (OH) ⁻ , HSO ₄ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , HCO ₃ ⁻ , H ₂ PO ₄ ⁻ , CH ₃ CO ₂ ⁻ , halogen ions (Cl ⁻ , Br ⁻ , I ^{− and the} like) and the like.

  Specific examples include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

  Examples of the sulfonium salt include those represented by the sulfonium salt represented by the following general formula (VI) and the following general formula (VII).

式中、Ｒ¹⁷〜Ｒ¹⁹は、それぞれ独立に、炭素数１〜２０のアルキル基、炭素数５〜１２のシクロアルキル基、炭素数３〜１２のアルケニル基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、又は炭素数１〜２０のアルコキシ基であり、さらに、置換基を有していてもよい。また、Ｒ¹⁷〜Ｒ¹⁹のうちの２個が互いに結合して、Ｎ、Ｐ、Ｏ、又はＳ原子を含む複素環を形成していてもよい。Ｚ^-は対イオンを表し、ＢＦ₄ ^-、ＡｓＦ₆ ^-、ＳｂＦ₆ ^-、ＳｂＣｌ₆ ^-、（Ｃ₆Ｆ₅）₄Ｂ^-、ＳｂＦ₅（ＯＨ）^-、ＨＳＯ₄ ^-、ｐ−ＣＨ₃Ｃ₆Ｈ₄ＳＯ₃ ^-、ＨＣＯ₃ ^-、Ｈ₂ＰＯ₄ ^-、ＣＨ₃ＣＯ₂ ^-、ハロゲンイオン（Ｃｌ^-、Ｂｒ^-、Ｉ^-等）などから選ばれる。

In the formula, R ^{17 to} R ¹⁹ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and may further have a substituent. Two of R ^{17 to} R ¹⁹ may be bonded to each other to form a heterocyclic ring containing an N, P, O, or S atom. Z ⁻ represents a counter ion, BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , SbF ₅ (OH) ⁻ , HSO ₄ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , HCO ₃ ⁻ , H ₂ PO ₄ ⁻ , CH ₃ CO ₂ ⁻ , halogen ions (Cl ⁻ , Br ⁻ , I ^{− and the} like) and the like.

式中、Ｒ²⁰〜Ｒ²¹は、それぞれ独立に、炭素数１〜２０のアルキル基、炭素数５〜１２のシクロアルキル基、炭素数３〜１２のアルケニル基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、又は炭素数１〜２０のアルコキシ基であり、さらに、置換基を有していてもよい。また、Ｒ²⁰〜Ｒ²¹のうちの２個が互いに結合して、Ｎ、Ｐ、Ｏ、又はＳ原子を含む複素環を形成していてもよい。また、Ａｒは置換基を有してよいアリール基を表す。Ａ^-は対イオンを表し、ＢＦ₄ ^-、ＡｓＦ₆ ^-、ＳｂＦ₆ ^-、ＳｂＣｌ₆ ^-、（Ｃ₆Ｆ₅）₄Ｂ^-、ＳｂＦ₅（ＯＨ）^-、ＨＳＯ₄ ^-、ｐ−ＣＨ₃Ｃ₆Ｈ₄ＳＯ₃ ^-、ＨＣＯ₃ ^-、Ｈ₂ＰＯ₄ ^-、ＣＨ₃ＣＯ₂ ^-、ハロゲンイオン（Ｃｌ^-、Ｂｒ^-、Ｉ^-等）などから選ばれる。

In the formula, R ^{20 to} R ²¹ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and may further have a substituent. Further, two of R ^{20 to} R ²¹ may be bonded to each other to form a heterocyclic ring containing N, P, O, or S atoms. Ar represents an aryl group which may have a substituent. A ⁻ represents a counter ion, BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , SbF ₅ (OH) ⁻ , HSO ₄ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , HCO ₃ ⁻ , H ₂ PO ₄ ⁻ , CH ₃ CO ₂ ⁻ , halogen ions (Cl ⁻ , Br ⁻ , I ^{− and the} like) and the like.

  Specifically, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl) sulfonium Hexafluoroarsinate and the like can be mentioned.

  There are commercially available onium salts such as Adeka Opton CP-66 and Adeka Opton CP-77 (manufactured by ADEKA), Sun Aid SI-60L, Sun Aid SI-80L and Sun Aid SI-100L (Sanshin Chemical Industry ( And CI series (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

  Among these photo and thermal cationic polymerization initiators, onium salts are preferred in that they are excellent in handleability and the balance between storage stability and curability, and among them, diazonium salts, iodonium salts, sulfonium salts, and phosphonium salts. Is particularly preferable in that it is excellent in handleability and the balance between storage stability and curability.

  The amount of the cationic polymerization initiator used is not particularly limited, depending on the reactivity of the initiator, the viscosity of the epoxy group-containing ester compound represented by the general formula (I) to be used, and the amount of the epoxy group in the ester compound. Depending on the ester compound having two or more alicyclic epoxy groups in one molecule to be used, generally from 0.01 to 15 parts by mass, more preferably Add in an amount of 0.05-5 parts by weight. Outside this range, the balance between the heat resistance and moisture resistance of the cured product after cationic polymerization is deteriorated, which is not preferable.

  Also in the curable composition containing the said polymerization initiator, other epoxy group containing compounds other than an epoxy group containing ester compound can be used together similarly to the case of the curable composition containing the above-mentioned hardening | curing agent. Further, if necessary, various additives (antioxidants, ultraviolet absorbers, metal oxides, silicon compounds, metal hydroxides, powder fillers) as in the case of the curable composition containing the above-described curing agent. , Colorants or pigments, flame retardants, ion adsorbents, coupling agents). These blending ratios are also the same as in the case of the curable composition containing the aforementioned curing agent.

  In addition, in the curable composition containing the above polymerization initiator, curable monomers such as diols or triols, vinyl ethers, oxetane compounds, and synthetic resins such as oligomers may be blended. The addition amount of the curable monomer and the oligomer is preferably 50 parts by mass or less with respect to 100 parts by mass of the total amount of the epoxy group-containing compound in the composition.

  The curable composition of the present invention may be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. More specifically, for example, a predetermined amount of the above-described components are uniformly stirred and mixed, dispersed and kneaded using an apparatus such as a planetary mixer, a triple roll, a two-heat roll, or a laika machine, and then under vacuum. Can be manufactured by defoaming.

  By curing the curable composition produced by the above method, a cured product having good electrical insulation characteristics can be obtained. When the curable composition of the present invention contains a curing agent or a curing accelerator in the curable composition, the optimal curing temperature condition varies depending on the type, but is generally performed at 40 to 200 ° C. , Preferably it is 50-185 degreeC. When the temperature is 40 ° C. or lower, the curing may not proceed sufficiently. When the temperature is 200 ° C. or higher, the curing reaction proceeds rapidly, and a large stress strain may occur in the cured product. The curing time depends on the type of curing agent and curing accelerator used and the composition ratio of the composition, but it is preferably heated for 0.5 hour or longer, more preferably 1 hour or longer. When the curing time is less than 0.5 hours, the curing may not be sufficiently advanced. The curing temperature is preferably raised stepwise. For example, if heating is performed at 120 ° C. for 3 hours after heating at 100 ° C. for 3 hours, the mechanical strength is simply increased compared to heating at 110 ° C. for 6 hours. An excellent cured product can be obtained. The cured product obtained by such a method has good electrical insulation characteristics.

  When the curable composition contains a cationic polymerization initiator, it may be thermally cured using a thermal cationic polymerization initiator as the cationic polymerization initiator, or may be photocured using a photocationic polymerization initiator.

  When heat curing is performed using a thermal cationic polymerization initiator, the curing reaction is performed at a temperature higher than the temperature at which the thermal cationic polymerization initiator starts the generation of cationic species and Lewis acid, preferably at 40 to 200 ° C. More preferably, it is 50-185 degreeC. When the temperature is 40 ° C. or lower, the curing may not proceed sufficiently. When the temperature is 200 ° C. or higher, the curing reaction proceeds rapidly, and a large stress strain may occur in the cured product. The curing time depends on the kind of the thermal cationic polymerization initiator used and the composition ratio of the composition, but it is preferable to heat for 10 minutes or more, and more preferably for 1 hour or more. When the curing time is less than 0.5 hours, the curing may not be sufficiently advanced. The curing temperature is preferably raised stepwise. For example, if heating is performed at 120 ° C. for 3 hours after heating at 100 ° C. for 3 hours, the mechanical strength is simply increased compared to heating at 110 ° C. for 6 hours. An excellent cured product can be obtained.

  When photocuring using a photocationic polymerization initiator, the curing reaction is performed by irradiating light having a photosensitive wavelength of the photocationic polymerization initiator. Examples of visible light or ultraviolet light sources used for light irradiation include low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, deuterium lamps, metal halide lamps, halogen lamps, xenon lamps, tungsten lamps, gallium lamps, and carbon arcs. A lamp, an incandescent bulb, a fluorescent lamp, an excimer lamp, a laser, or the like can be used. Of these light sources, a high-pressure mercury lamp and a metal halide lamp are particularly preferable.

The wavelength of the visible light or ultraviolet curing light source is usually 200 nm to 750 nm, preferably 200 nm to 450 nm, and the irradiation amount is usually 50 mJ / cm ^{2 to} 2000 mJ / cm ² , preferably 100 mJ / cm ^{2 to} 1500 mJ / cm ^2. It is.

  In curing using an electron beam, examples of the irradiation method include a scanning method, a broad beam method, a curtain beam method, and an ion plasma method, and the irradiation amount is usually 0.1 Gy to 200 kGy, and 1 Gy to 100 kGy is preferred.

  The cured product obtained by such a method is a cured product having good electrical insulation characteristics.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited only to a following example.
<Measurement of epoxy equivalent>
The epoxy equivalent was measured according to JIS K7236.

(Execution synthesis example A-1)
In a 1000 ml three-necked round bottom flask equipped with a stirrer, a thermometer and a rectifying column, 600.0 g (3.29 mol) of allyl 3,4-epoxycyclohexane-1-carboxylate and tricyclo [5.2.1.0] were added. ^2,6 ] decanedimethanol 323.2 g (1.65 mol) and dibutyltin oxide 1.84 g were added, and the reaction was carried out by heating in an oil bath adjusted to 130 ° C. under a nitrogen stream. As the reaction proceeds, allyl alcohol produced is distilled from the rectifying column and obtained in a 300 ml eggplant type flask. As the reaction proceeds, the pressure in the 1000 ml three-necked round bottom flask is gradually reduced. Time reaction was performed. The distillation amount of allyl alcohol was 180 g (92.1% of the theoretical amount). After completion of the reaction, the pressure was reduced to 400 Pa, and unreacted allyl 3,4-epoxycyclohexane-1-carboxylate was distilled off to obtain a pale yellow viscous liquid product (hereinafter also referred to as “product A1”). .

By gas chromatography analysis of the product A1 (hereinafter also referred to as “GC analysis”), tricyclo [5.2.1.0 ^2,6 ] decanedimethanol was below the detection limit. Further, it was confirmed by GC analysis of the product A1 that 5.8% by mass of allyl 3,4-epoxycyclohexane-1-carboxylate remained. The epoxy equivalent of product A1 was 250.5 g / eqV.

When the product A1 was analyzed by ¹ H-NMR (tetramethylsiloxane: 0.1 mass ppm was used as the internal standard substance), 78.0% by mass of the product A1 is represented by the structural formula (1). The compound, 16.2% by mass, was a compound represented by the structural formula (16). The ¹ H-NMR (solvent: CDCl ₃ ) and IR spectrum of the product A1 are shown in FIGS. 1 and 2, respectively.

¹Ｈ−ＮＭＲスペクトルの主な帰属は、以下の通りである（アンダーラインを付けた水素が該当プロトンであることを意味する）。

The main assignment of the ¹ H-NMR spectrum is as follows (meaning that the underlined hydrogen is the relevant proton).

_{4.6ppm (CH 2 = CHC H 2} OCO- unreacted 3,4-epoxycyclohexane-1-carboxylic acid allyl),
3.3~3.6ppm (-C H ₂ OH of the compound represented by the structural formula (16)),
3.81~4.26ppm (-C H ₂ OCO-),
3.16 to 3.26 ppm ( H of 3,4-epoxycyclohexane ring (Structural Formula (17)))

０．９５〜２．５３ｐｐｍ（トリシクロ［５．２．１．０^2,6］デカン環の環状の全ての ＞ＣＨ−、−ＣＨ ₂− 及び ３，４−エポキシシクロヘキサン環（構造式（１８）)のＨ）

0.95～2.53Ppm (tricyclo [5.2.1.0 ^{2, 6]} decane ring all the annular> C H -, - C H 2 - and 3,4-epoxy cyclohexane ring (structure ( 18)) H )

また、ＩＲスペクトルの主な帰属は以下の通りである。

The main attribution of the IR spectrum is as follows.

Absorption band around 3530cm ^-1 (OH expansion and contraction)
Absorption bands around 2946 cm ^-1 and 2876 cm ^-1 (CH ₂ stretching)
Absorption band near 1731 cm ^-1 (carboxylic acid ester C = O stretch)
Absorption bands near 1456 cm ^-1 and 1437 cm ^-1 (CH ₂ variable angle)
Absorption band around 1137 cm ⁻¹ (CO stretching of carboxylate ester)
(Execution synthesis example A-2)
In a 2000 ml three-necked round bottom flask equipped with a stirrer, a thermometer and a rectification column, 669.9 g (3.68 mol) of allyl 3,4-epoxycyclohexane-1-carboxylate, hydrogenated dimer diol (product of Cognis) Name: Sovermol 908 (hydroxyl value 209 mgKOH / g) 886.8 g and dibutyltin oxide 3.16 g were added, and the reaction was carried out by heating in an oil bath adjusted to 130 ° C. As the reaction proceeds, allyl alcohol produced is distilled from the rectifying column and obtained in a 500 ml eggplant type flask. As the reaction proceeds, the inside of the 2000 ml three-necked round bottom flask is gradually depressurized and reacted for 8 hours. Went. The amount of allyl alcohol distilled was 191.0 g (99.6% of the theoretical amount). After completion of the reaction, the pressure was reduced to 400 Pa, and unreacted allyl 3,4-epoxycyclohexane-1-carboxylate was distilled off to obtain a pale yellow viscous liquid product (hereinafter also referred to as “product A2”). .

  By liquid chromatography analysis of the product A2 (hereinafter also referred to as “LC analysis”), the hydrogenated dimer diol was below the detection limit. Further, it was confirmed by GC analysis of the product A2 that 3.1% by mass of allyl 3,4-epoxycyclohexane-1-carboxylate remained. Moreover, the epoxy equivalent of the product A2 was 396.4 g / eqV.

Analysis of product A2 by ¹ H-NMR revealed that 96.0% by mass of product A2 was exchanged with 3,4-epoxycyclohexane-1-carboxylate at both ends (structure (2)). 0.9% by mass was a compound in which one end was a hydroxyl group and the other end was 3,4-epoxycyclohexane-1-carboxylate. The ¹ H-NMR (solvent: CDCl ₃ ) and IR spectrum of the product A2 are shown in FIGS. 3 and 4, respectively.

The main assignment of the ¹ H-NMR spectrum is as follows (meaning that the underlined hydrogen is the relevant proton).
_{4.6ppm (CH 2 = CHC H 2} OCO- unreacted 3,4-epoxycyclohexane-1-carboxylic acid allyl),
3.6ppm (C H ₂ OH mono 3,4-epoxycyclohexane-1-carboxylate of hydrogenated dimer diol),
4.05ppm (-C H ₂ OCO-),
3.16 to 3.23 ppm (3,4-epoxycyclohexane ring ( H 2 in structural formula (17))
0.84 to 2.54 ppm (CH ₂ of alkylene derived from hydrogenated dimerdiol, CH ₂ and 3,4-epoxycyclohexane ring ( H ₂ of structural formula (18)))
The main attribution of the IR spectrum is as follows.

Absorption band around 3448cm ^-1 (OH expansion and contraction)
Absorption bands around 2926 cm ^-1 and 2854 cm ^-1 (CH ₂ stretching)
Absorption band around 1734 cm ⁻¹ (C═O stretching of carboxylate ester)
Absorption bands near 1459 cm ^-1 and 1434 cm ^-1 (CH ₂ variable angle)
Absorption band near 1172 cm ^-1 (CO stretching of carboxylate ester)
(Execution synthesis example A-3)
In a 2000 ml three-necked round bottom flask equipped with a stirrer, thermometer and rectifying column, 500.0 g (2.74 mol) of allyl 3,4-epoxycyclohexane-1-carboxylate and alkanediol having 9 carbon atoms as raw materials Polycarbonate diol (trade name: Kuraray polyol C-1015N, hydroxyl value 116.4 mgKOH / g) 1300 g and dibutyltin oxide 3.60 g were added and heated in an oil bath adjusted to 130 ° C. under a nitrogen stream. The reaction was carried out. As the reaction proceeds, allyl alcohol produced is distilled from the rectification column and obtained in a 300 ml eggplant type flask. As the reaction proceeds, the pressure in the 2000 ml three-necked round bottom flask is gradually reduced. Time reaction was performed. The distillation amount of allyl alcohol was 155.2 g (99.1% of the theoretical amount). After completion of the reaction, the pressure was reduced to 400 Pa, and unreacted allyl 3,4-epoxycyclohexane-1-carboxylate was distilled off to obtain a pale yellow viscous liquid product (hereinafter also referred to as “product A3”). .

  By LC analysis of product A3, polycarbonate diol was below the detection limit. Further, it was confirmed by GC analysis of the product A3 that 0.5% by mass of allyl 3,4-epoxycyclohexane-1-carboxylate remained. The epoxy equivalent of product A3 was 609.0 g / eqV.

When product A3 was analyzed by ¹ H-NMR (tetramethylsiloxane: 0.1 mass ppm used as the internal standard substance), 94.7 mass% of product A3 is represented by structural formula (3). The compound, 3.5% by mass, was a compound represented by the structural formula (19). The ¹ H-NMR (solvent: CDCl ₃ ) and IR spectrum of the product A3 are shown in FIGS. 5 and 6, respectively.

¹Ｈ−ＮＭＲスペクトルの主な帰属は、以下の通りである（アンダーラインを付けた水素が該当プロトンであることを意味する。）。

The main assignment of the ¹ H-NMR spectrum is as follows (meaning that the underlined hydrogen is the relevant proton).

_{4.6ppm (CH 2 = CHC H 2} OCO- unreacted 3,4-epoxycyclohexane-1-carboxylic acid allyl),
_{3.87~4.13ppm (-C H 2 OCO -,} - C H 2 OCOOC H 2 -),
3.6~3.7ppm (-C H ₂ OH of the compound represented by the structural formula (19)),
3.16 to 3.25 ppm ( H of 3,4-epoxycyclohexane ring (Structural Formula (17)))
1.17～2.53Ppm (poly (-CH ₂ -C H in alkylene carbonate) structural units _{(CH 3) -CH 2, -CH} 2 -C H 2 -CH 2 -, - CH (CH 3) - C H ₂ —CH ₂ — and 3,4-epoxycyclohexane ring ( H in structural formula (18))
0.93 to 0.96 ppm (—CH (C H ₃ ) — in the poly (alkylene carbonate) structural unit)
The main attribution of the IR spectrum is as follows.

Absorption band around 3467cm ^-1 (OH expansion and contraction)
Absorption bands around 2932 cm ^-1 and 2857 cm ^-1 (CH ₂ stretching)
Absorption band near 1744cm ^-1 (C = O stretching of carbonate part)
Absorption band near 1258cm ^-1 (CO stretch of carbonate part)
(Comparative Synthesis Example A-1)
In a 2000 ml separable flask equipped with a stirrer, a thermometer, and a rectifying column, 1,55.03 g (8.53 mol) of allyl 3,4-epoxycyclohexane-1-carboxylate and 384.70 g (4. 27 mol) and 3.86 g of dibutyltin oxide were added, and the reaction was carried out by adjusting and heating the oil bath so that the internal temperature in the flask was 127 to 128 ° C. As the reaction proceeds, allyl alcohol produced is distilled from the rectification column and obtained in a 500 ml eggplant type flask. As the reaction proceeds, a diaphragm pump is connected gradually through a liquid nitrogen trap. The reaction was carried out under reduced pressure for 5 hours. The distillation amount of allyl alcohol was 456.7 g (92.1% of the theoretical amount). After completion of the reaction, the pressure was reduced to 400 Pa, and unreacted allyl 3,4-epoxycyclohexane-1-carboxylate was distilled off to obtain a light red-brown viscous liquid product (hereinafter also referred to as “product A4”).

  According to GC analysis of product A4, 1,4-butanediol was below the detection limit. In addition, GC analysis of the product A4 confirmed that 5.1% by mass of allyl 3,4-epoxycyclohexane-1-carboxylate remained. The epoxy equivalent of product A4 was 185.5 g / eqV.

^When analyzed by ¹ H-NMR, 91.2% by mass of the product A5 is a compound represented by the structural formula (20), and 3.7% by mass is a compound represented by the structural formula (21). Was confirmed.

（実施配合例１）
生成物Ａ１ １００ｇ、カチオン重合開始剤（三新化学工業（株）製 商品名；サンエイドＳＩ−１００Ｌ）１．００ｇ、シリコーン系消泡剤（商品名：ＴＳＡ７５０Ｓ、ＧＥ・東芝シリコーン（株）社製）１．４０ｇを混合し、ハイブリッドミキサー（グレード名：ＨＭ−５００（株）キーエンス製）で５分間撹拌、１０分間脱泡処理を行った。この配合物を配合組成Ｂ１とした。

(Example formulation 1)
Product A1 100 g, cationic polymerization initiator (trade name; San-Aid SI-100L, manufactured by Sanshin Chemical Industry Co., Ltd.), silicone antifoaming agent (trade name: TSA750S, manufactured by GE / Toshiba Silicone Co., Ltd.) 1.40 g was mixed, stirred for 5 minutes with a hybrid mixer (grade name: HM-500, manufactured by Keyence Corporation), and defoamed for 10 minutes. This blend was designated as blend composition B1.

(Example formulation examples 2 to 6 and comparative formulation examples 1 to 4)
It mix | blended according to the mixing | blending composition shown in Table 1, and prepared the mixture by carrying out stirring for 5 minutes and defoaming for 10 minutes with a hybrid mixer (grade name: HM-500 Co., Ltd. product made from Keyence). The blends prepared in Examples 2-6 were blended compositions B2-B6, respectively, and the blends blended in Comparative Blend Examples 1-4 were set as comparative blend compositions B1-B4, respectively. In addition, the unit of the number of each component of the implementation formulation examples 1 to 6 and the comparative formulation examples 1 to 4 described in Table 1 is “g”.

長期電気絶縁信頼性試験（配合組成Ｂ１〜Ｂ６及び比較配合組成Ｂ１〜Ｂ４）
フレキシブル銅張り積層板（商品名：ＵＰＩＳＥＬ−Ｎ ＢＥ１３１０（グレード名）、宇部興産（株）製）をエッチングして製造した櫛形基板（銅配線幅／銅配線間幅＝５０μｍ／５０μｍ）に、上記配合組成Ｂ１を、ガラス棒を用いて、５０μｍの厚さ（乾燥後）になるように塗布（配線接続部は除く）した。その後、熱風循環式乾燥機を用いて、１００℃×１時間、１２０℃×１時間、１５０℃×１時間と、段階的に温度を上げて硬化させ、試験片を得た。

Long-term electrical insulation reliability test (composition composition B1-B6 and comparison composition B1-B4)
A comb-shaped substrate (copper wiring width / copper wiring width = 50 μm / 50 μm) manufactured by etching a flexible copper-clad laminate (trade name: UPISEL-N BE1310 (grade name), manufactured by Ube Industries, Ltd.) Formulation composition B1 was applied (excluding the wiring connection portion) to a thickness of 50 μm (after drying) using a glass rod. Thereafter, using a hot air circulation dryer, the temperature was gradually increased and cured at 100 ° C. × 1 hour, 120 ° C. × 1 hour, and 150 ° C. × 1 hour to obtain a test piece.

  In addition, a comb-shaped substrate (copper wiring width / width) manufactured by etching a flexible copper-clad laminate (trade name: UPISEL-N BE1310 (grade name), manufactured by Ube Industries, Ltd.) in the same manner as in the above-described composition B1. Copper wiring width = 50 [mu] m / 50 [mu] m), and coating composition B2 to B6 and comparative blending composition B1 to B4 using a glass rod to a thickness of 50 [mu] m (after drying) (excluding wiring connection part) And cured using a hot air circulation dryer at the temperature and time shown in Table 2 to obtain a test piece.

  Next, using the test pieces obtained from the blending compositions B1 to B6 and the comparative blending compositions B1 to B4, a bias voltage of 100 V was applied, and the temperature and humidity steady state test (at a temperature of 85 ° C. and a humidity of 85% RH) ( A long-term electrical insulation reliability test) was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV Corporation). In the above temperature and humidity steady test, the initial value of the start (initial resistance value: [Ω]), 500 hours after the start (resistance value after 500 hours: [Ω]) and 1000 hours after the resistance value (after 1000 hours) Resistance value: [Ω] was measured, and the results are shown in Table 2.

表２の結果より、本発明の一般式（Ｉ）で表されるエポキシ基含有エステル化合物を含む硬化性組成物を硬化させることによって、高いレベルでの長期電気絶縁特性を有する硬化物を提供できることが示唆される。

From the results of Table 2, it is possible to provide a cured product having a long-term electrical insulation characteristic at a high level by curing a curable composition containing an epoxy group-containing ester compound represented by the general formula (I) of the present invention. Is suggested.

Claims (11)

A curable composition containing an epoxy group-containing ester compound represented by the following general formula (I).

(In the formula, R ¹ represents an organic residue derived from a (poly) carbonate polyol having a structural unit derived from an alkanediol having a branched structure and / or a cyclic structure having 9 or more carbon atoms. R ² represents each. Independently represents H or CH ₃ , R ³ and R ⁴ each independently represents an OR group or an OH group, where R is an organic residue, m is an integer of 1 to 4, and n is 0 to 3 Integer, l represents an integer of 0 to 3) The curable composition according to claim 1, further comprising an alicyclic epoxy group-containing carboxylic acid ester represented by the following general formula (II).

(In the formula, R ⁵ represents H or CH ₃ , and R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.) Furthermore, the epoxy group containing ester compound represented by following formula (3) is included, The curable composition of Claim 1 or 2 characterized by the above-mentioned.

(In the formula, o represents an integer of 0 or more, p represents an integer of 0 or more, and o + p is a natural number of 1 or more.) Furthermore, the compound represented by following Structural formula (16) is included, The curable composition of Claim 3 characterized by the above-mentioned.

  The curable composition according to any one of claims 1 to 4, further comprising a curing agent or a polymerization initiator. The alicyclic epoxy group-containing carboxylic acid ester represented by the following general formula (II) and a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and the total number of carbon atoms is 12 or more The curing according to claim 1, comprising a step of producing an epoxy group-containing ester compound represented by the general formula (I) by reacting with a polyhydric alcohol using a transesterification catalyst. Method for producing a composition.

(In the formula, R ⁵ represents H or CH ₃ , and R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms.)   The polyhydric alcohol containing a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms and having a total of 12 or more carbon atoms has a branched structure and / or a cyclic structure having 9 or more carbon atoms. The method for producing a curable composition according to claim 6, which is a (poly) carbonate polyol having a structural unit derived from alkanediol.   The curable composition according to claim 6 or 7, wherein the transesterification catalyst is at least one compound selected from the group of dialkyltin oxides, tetraalkyl titanates and metal acetylacetonate complexes. Manufacturing method.   The method for producing a curable composition according to claim 6 or 7, wherein the transesterification catalyst is dibutyltin oxide or dioctyltin oxide.   The transesterification catalyst is used in an amount that includes an alicyclic epoxy group-containing carboxylic acid ester and a saturated hydrocarbon chain having a branched structure and / or a cyclic structure having 9 or more carbon atoms, and the total number of carbon atoms is 12 or more. It is 0.01-3.0 mass% with respect to the total amount of a monohydric alcohol, The manufacturing method of the curable composition of any one of Claims 6-9 characterized by the above-mentioned. An epoxy group-containing ester compound represented by the following formula (3).

(In the formula, o represents an integer of 0 or more, p represents an integer of 0 or more, and o + p is a natural number of 1 or more.)

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