JPWO2017077845A1 - Polyfunctional epoxy compound and curable composition containing the same - Google Patents

Abstract

Provided is a polyfunctional epoxy compound which has a low dielectric constant and can achieve a sufficiently low dielectric constant of a cured epoxy resin obtained from the composition when added to a general-purpose epoxy resin composition. about. An epoxy compound represented by the formula [1]. Wherein R1 represents an alkyl group having 2 to 30 carbon atoms, R2 to R4 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L represents a carbonyl group. Or A represents a methylene group, A represents an aliphatic hydrocarbon group which may contain a (n + 1) -valent ether bond, and n represents an integer of 2 to 8.) [Selection] None

Description

  The present invention relates to a polyfunctional epoxy compound, a curable composition containing the same, and a method for producing the epoxy compound. More specifically, the present invention relates to a curable composition for obtaining a cured product having a low dielectric constant and a polyfunctional epoxy compound contained therein. Moreover, it is related with the manufacturing method of the polyfunctional epoxy compound which can reduce the dielectric constant of the hardened | cured material obtained from this composition by adding to a general purpose epoxy resin composition, and the polyfunctional epoxy compound.

  Conventionally, an epoxy resin is an epoxy resin composition combined with a curing agent or a curing catalyst, such as an adhesive, a high refractive index layer of an antireflection film (such as an antireflection film for a liquid crystal display), or an optical thin film (such as a reflection plate). It is widely used in the field of electronic materials such as encapsulants for electronic components, printed wiring boards, and interlayer insulating film materials (such as interlayer insulating film materials for build-up printed boards). Among such electronic materials, in applications such as printed wiring boards and interlayer insulation film materials, in addition to high adhesion to substrates, hard coat properties, heat resistance, high transparency to visible light, etc., in recent years electronic devices Therefore, it is required to have a low dielectric constant in order to suppress electrical signal delay and to adjust capacitance. However, the cured epoxy resin generally has a high polarity, and it has been difficult to achieve a sufficiently low dielectric constant.

  Up to now, as a method for reducing the dielectric constant of a cured epoxy resin, a hollow particle is added to the epoxy resin composition, and an air layer is included in the cured product obtained from the composition so that the cured product has a low dielectric constant. There is known a method of making it (for example, Patent Document 1).

JP 2010-285624 A

However, in the method described in Patent Document 1, since hollow particles are added to the composition, the optical properties, mechanical properties, thermal properties, and the like of the base resin are changed, which may adversely affect the material design.
The present invention takes this situation into consideration, and has a low dielectric constant, and when added to a general-purpose epoxy resin composition, the epoxy resin cured product obtained from the composition has a sufficiently low dielectric constant. It aims at providing the polyfunctional epoxy compound which can be achieved.
Another object of the present invention is to provide a curable composition for forming a cured product having a low dielectric constant, which can be used in the field of electrical materials such as printed wiring boards, and an epoxy compound contained in the composition. To do.
Moreover, an object of this invention is to provide the manufacturing method of the said epoxy compound.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cured product obtained from a curable composition containing a polyfunctional epoxy compound having a specific structure exhibits a low dielectric constant. The headline and the present invention were completed.

（式中、Ｒ^１は炭素原子数２乃至３０のアルキル基を表し、Ｒ^２乃至Ｒ^４はそれぞれ独立して、水素原子又は炭素原子数１乃至１０のアルキル基を表し、Ｌはカルボニル基又はメチレン基を表し、Ａは（ｎ＋１）価のエーテル結合を含んでいてもよい脂肪族炭化水素基を表し、ｎは２乃至８の整数を表す。）、
第２観点として、前記Ｒ^１が炭素原子数６乃至２６のアルキル基を表す、第１観点に記載のエポキシ化合物、
第３観点として、前記Ｒ^１が炭素原子数１４乃至２０のアルキル基を表す、第２観点に記載のエポキシ化合物、
第４観点として、前記Ｒ^１が分岐鎖アルキル基である、第１観点乃至第３観点のうち何れか一つに記載のエポキシ化合物、
第５観点として、前記Ａが、グリセリン、２−ヒドロキシ−１，４−ブタンジオール、トリメチロールメタン、１，１，１−トリメチロールエタン、１，１，１−トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、及びジペンタエリスリトールからなる群から選ばれるポリオールからヒドロキシ基を除いて誘導される基である、第１観点乃至第４観点のうち何れか一つに記載のエポキシ化合物、
第６観点として、前記Ａが、１，１，１−トリメチロールプロパン、及びペンタエリスリトールからなる群から選ばれるポリオールからヒドロキシ基を除いて誘導される基である、第５観点に記載のエポキシ化合物、
第７観点として、（ａ）第１観点乃至第６観点のうち何れか一つに記載のエポキシ化合物、及び（ｂ）硬化剤を含む、硬化性組成物、
第８観点として、前記（ｂ）硬化剤が、酸無水物、アミン、フェノール樹脂、ポリアミド樹脂、イミダゾール類、及びポリメルカプタンからなる群から選ばれる少なくとも一種である、第７観点に記載の硬化性組成物、
第９観点として、前記（ａ）エポキシ化合物のエポキシ基１当量に対して、０．５〜１．５当量の前記（ｂ）硬化剤を含む、第７観点又は第８観点に記載の硬化性組成物、
第１０観点として、（ａ）第１観点乃至第６観点のうち何れか一つに記載のエポキシ化合物、及び（ｃ１）酸発生剤及び／又は（ｃ２）塩基発生剤からなる（ｃ）硬化触媒を含む、硬化性組成物、
第１１観点として、前記（ｃ）硬化触媒が（ｃ１）酸発生剤である、第１０観点に記載の硬化性組成物、
第１２観点として、前記（ｃ１）酸発生剤が、光酸発生剤、及び熱酸発生剤からなる群から選ばれる少なくとも一種である、第１１観点に記載の硬化性組成物、
第１３観点として、前記（ｃ１）酸発生剤がオニウム塩である、第１２観点に記載の硬化性組成物、
第１４観点として、前記（ｃ１）酸発生剤が、スルホニウム塩、又はヨードニウム塩である、第１３観点に記載の硬化性組成物、
第１５観点として、前記（ａ）エポキシ化合物１００質量部に対して、前記（ｃ１）酸発生剤０．１〜２０質量部を含む、第１１観点乃至第１４観点のうち何れか一項に記載の硬化性組成物、
第１６観点として、式［２］で表されるエン化合物を酸化することを特徴とする、式［１］で表されるエポキシ化合物の製造方法、

（式中、Ｒ^１は炭素原子数２乃至３０のアルキル基を表し、Ｒ^２乃至Ｒ^４はそれぞれ独立して、水素原子又は炭素原子数１乃至１０のアルキル基を表し、Ｌはカルボニル基又はメチレン基を表し、Ａは（ｎ＋１）価のエーテル結合を含んでいてもよい脂肪族炭化水素基を表し、ｎは２乃至８の整数を表す。）

（式中、Ｒ^１、Ｒ^２乃至Ｒ^４、Ｌ、Ａ、ｎは前記と同じ意味を表す。）、
に関する。That is, the present invention provides, as a first aspect, an epoxy compound represented by the formula [1],

(Wherein R ¹ represents an alkyl group having 2 to 30 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L represents a carbonyl group or Represents a methylene group, A represents an aliphatic hydrocarbon group which may contain an (n + 1) -valent ether bond, and n represents an integer of 2 to 8.
As a second aspect, the epoxy compound according to the first aspect, wherein R ¹ represents an alkyl group having 6 to 26 carbon atoms,
As a third aspect, the epoxy compound according to the second aspect, wherein R ¹ represents an alkyl group having 14 to 20 carbon atoms,
As a fourth aspect, the epoxy compound according to any one of the first to third aspects, wherein R ¹ is a branched alkyl group,
As a fifth aspect, the A is glycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, ditrimethylolpropane, The epoxy compound according to any one of the first to fourth aspects, which is a group derived by removing a hydroxy group from a polyol selected from the group consisting of pentaerythritol and dipentaerythritol,
As a sixth aspect, the epoxy compound according to the fifth aspect, wherein A is a group derived by removing a hydroxy group from a polyol selected from the group consisting of 1,1,1-trimethylolpropane and pentaerythritol. ,
As a seventh aspect, (a) a curable composition containing the epoxy compound according to any one of the first aspect to the sixth aspect, and (b) a curing agent,
As an eighth aspect, the curability according to the seventh aspect, in which the (b) curing agent is at least one selected from the group consisting of acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, and polymercaptans. Composition,
As 9th viewpoint, the sclerosis | hardenability as described in 7th viewpoint or 8th viewpoint containing 0.5-1.5 equivalent of said (b) hardening | curing agent with respect to 1 equivalent of epoxy groups of said (a) epoxy compound. Composition,
As a tenth aspect, (c) a curing catalyst comprising (a) the epoxy compound according to any one of the first to sixth aspects, and (c1) an acid generator and / or (c2) a base generator. A curable composition comprising
As an eleventh aspect, the curable composition according to the tenth aspect, in which the (c) curing catalyst is (c1) an acid generator,
As a twelfth aspect, the curable composition according to the eleventh aspect, wherein the (c1) acid generator is at least one selected from the group consisting of a photoacid generator and a thermal acid generator,
As a thirteenth aspect, the (c1) acid generator is an onium salt, and the curable composition according to the twelfth aspect,
As a fourteenth aspect, the curable composition according to the thirteenth aspect, in which the (c1) acid generator is a sulfonium salt or an iodonium salt,
As a fifteenth aspect, according to any one of the eleventh aspect to the fourteenth aspect, which includes 0.1 to 20 parts by mass of the acid generator (c1) with respect to 100 parts by mass of the (a) epoxy compound. A curable composition of
As a sixteenth aspect, a method for producing an epoxy compound represented by the formula [1], wherein the ene compound represented by the formula [2] is oxidized,

(Wherein R ¹ represents an alkyl group having 2 to 30 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L represents a carbonyl group or Represents a methylene group, A represents an aliphatic hydrocarbon group which may contain an (n + 1) -valent ether bond, and n represents an integer of 2 to 8.

(Wherein R ¹ , R ^{2 to} R ⁴ , L, A, and n have the same meaning as described above),
About.

Since the polyfunctional epoxy compound of the present invention has a higher alkyl group site in its structure, a cured product having a low dielectric constant can be obtained from a curable composition containing the epoxy compound and a curing agent or a curing catalyst. Can be obtained.
Moreover, since the polyfunctional epoxy compound of this invention reacts with the acid or base which generate | occur | produced from the conventional hardening | curing agent or the curing catalyst, and hardens | cures, it can be added to a general purpose epoxy resin composition. And the polyfunctional epoxy compound of this invention adds the dielectric constant of the epoxy resin hardened | cured material obtained from this composition by adding to an epoxy resin composition, from the epoxy resin composition which has not added a polyfunctional epoxy compound. It can be made lower than the dielectric constant of the resulting cured epoxy resin.
In addition, according to the present invention, a polyfunctional epoxy compound having a higher alkyl group can be produced.

[(A) Epoxy compound]
The present invention is an epoxy compound represented by the above formula [1].
In the above formula [1], R ¹ represents an alkyl group having 2 to 30 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L is Represents a carbonyl group or a methylene group, A represents an aliphatic hydrocarbon group which may contain an (n + 1) -valent ether bond, and n represents an integer of 2 to 8.

R ¹ in the formula [1] represents an alkyl group having 2 to 30 carbon atoms, preferably an alkyl group having 6 to 26 carbon atoms, more preferably an alkyl group having 14 to 20 carbon atoms. Examples of the alkyl group include a straight chain alkyl group, a branched chain alkyl group, and an alicyclic group, preferably a branched chain alkyl group, more preferably a branched chain alkyl group having 6 to 26 carbon atoms, and still more preferably carbon. Examples thereof include a branched alkyl group having 14 to 20 atoms.
When the epoxy compound represented by the formula [1] has an alkyl group having 2 to 30 carbon atoms, for example, a higher alkyl group, as R ¹ , the viscosity is lowered and the solubility in a low-polarity solvent is reduced. Can be further enhanced. Moreover, the epoxy compound which has a higher alkyl group can reduce the dielectric constant of the hardened | cured material obtained using this compound, and can make the flexibility high. Moreover, this compound can reduce the water absorption of the hardened | cured material obtained using this compound, and can improve the water repellency of the surface.

  Among the alkyl groups having 2 to 30 carbon atoms, examples of the linear alkyl group include an ethyl group, a propyl group, a butyl group, a pentyl group (amyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. , Undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (Aralkyl group), Henicosyl group, Docosyl group (Behenyl group), Tricosyl group, Tetracosyl group (Lignoceryl group), Pentacosyl group, Hexacosyl group, Heptacosyl group, Octacosyl group (Montanyl group), Nonacosyl group, Triaconyl group (Mellysyl group) Etc.

  Among the alkyl groups having 2 to 30 carbon atoms, examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl. Group, isohexyl group, texyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexane-2-yl group, 3-methylhexane-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl Group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5,5-to Methylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyl Octyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctane-4-yl group, 9-methyldecyl group, undecan-5-yl group, 3-ethylnonan-3-yl group, 5- Ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexane-4-yl group, 10-methylundecyl group, 11-methyldodecyl group, tridecan-6-yl group, tridecan-7- Yl group, 7-ethylundecan-2-yl group, 3-ethylundecan-3-yl group, 5-ethylundecan-5-yl group, 12-methyltridecyl group, 13-methyltetradecyl group , Pentadecan-7-yl group, pentadecan-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecan-8-yl group, heptadecan-9-yl group, 3,13-dimethylpentadecane- 7-yl group, 2,2,4,8,10,10-hexamethylundecan-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group, nonadecan-9-yl group, nonadecane-10- Yl group, 2,6,10,14-tetramethylpentadecan-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, heicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, Tricosane-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosane-12-i Group, pentacosan-13-yl group, 2,22-dimethyltricosan-11-yl group, 3,21-dimethyltricosan-11-yl group, 9,15-dimethyltricosan-11-yl group, 24 -Methylpentacosyl group, 25-methylhexacosyl group, heptacosane-13-yl group, 26-methylheptacosyl group, 27-methyloctacosyl group, nonacosan-14-yl group, 28-methylnonacosyl group, etc. Is mentioned.

Among the alkyl groups having 2 to 30 carbon atoms, the alicyclic group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-tert-butylcyclohexyl group, a 1,6-dimethylcyclohexyl group, and a menthyl group. , Cycloheptyl group, cyclooctyl group, bicyclo [2.2.1] heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo [5.2.1.0 ^{2 , 6} ] decan-4-yl group, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, cyclododecyl group and the like.

Preferable R ¹ is pentadecan-7-yl group, heptadecan-9-yl group, 3,13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecane-5 Yl group, 2,6,10,14-tetramethylpentadecan-7-yl group and pentacosan-12-yl group.

In the above formula [1], R ^{2 to} R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, and pentyl. Group (amyl group), isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, A decyl group etc. are mentioned.
Preferable R ^{2 to} R ⁴ include a hydrogen atom.

In the above formula [1], A represents a group which may contain an (n + 1) -valent ether bond.
As A, for example, an (n + 1) -valent group derived from the above alkyl group having 1 to 10 carbon atoms or an alkyl group having 2 to 30 carbon atoms by further removing (n) hydrogen atoms. Can be mentioned. These groups may contain an ether bond (—O—) between any carbon-carbon bonds.
Specifically, for example, glycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, ditrimethylolpropane, pentaerythritol And an (n + 1) -valent group derived by removing a hydroxy group from a polyol selected from the group consisting of dipentaerythritol.

（式中、Ａ及びＲ^２乃至Ｒ^４は前記と同じ意味を表す。）で表されるアルコールなどのアルコール誘導体とを反応させ、そして得られた不飽和結合を有する化合物（中間体）と過酸化物を反応させて、上記式［１］で表されるエポキシ化合物を製造することができる。
即ち、本発明の式［１］で表される化合物の製造は、以下の反応式［３］によって表される。

[Method for producing epoxy compound]
The compound represented by the formula [1] (L represents a carbonyl group) of the present invention is, for example, a carboxylic acid having the structure of R ¹ or an activated form thereof (acid halide, acid anhydride, acid azide, activity Esters) and alcohols having 2 to 8 allyl ether groups having the structure of A, ie, the formula

(Wherein A and R ^{2 to} R ⁴ represent the same meaning as described above) and an alcohol derivative such as an alcohol represented by the formula (A) and the resulting compound having an unsaturated bond (intermediate) An epoxy compound represented by the above formula [1] can be produced by reacting an oxide.
That is, the production of the compound represented by the formula [1] of the present invention is represented by the following reaction formula [3].

（式中、Ｒ^２乃至Ｒ^４は前記と同じ意味を表し、Ｘはヒドロキシ基、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、トルエンスルホニルオキシ基、ニトロベンゼンスルホニルオキシ基、アセトキシ基、トリフルオロアセトキシ基、塩素原子、臭素原子、又はヨウ素原子を表す。）The compound represented by the formula [1] (L represents a methylene group) of the present invention includes, for example, derivatives such as a compound having a structure of R ¹ and a leaving group X, and the above allyl ethers of 2 to 8. An epoxy compound represented by the above formula [1] can be produced by reacting an alcohol having a group and reacting the obtained compound (intermediate) having an unsaturated bond with a peroxide.
That is, the production of the compound represented by the formula [1] of the present invention is represented by the following reaction formula [4].

(Wherein R ^{2 to} R ⁴ represent the same meaning as described above, and X represents a hydroxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a toluenesulfonyloxy group, a nitrobenzenesulfonyloxy group, an acetoxy group, and a trifluoroacetoxy group. Represents a chlorine atom, a bromine atom, or an iodine atom.)

As the carboxylic acid having the structure of R ¹ , a commercially available carboxylic acid or an activated form thereof can be used. For example, a carboxylic acid such as Fine Oxocol (registered trademark) Isopalmitic acid, Isostearic acid, Isostearic acid N, Isostearic acid T, Isostearic acid T, and Isoarachic acid manufactured by Nissan Chemical Industries, Ltd., or a derivative of the carboxylic acid Can be mentioned.

Derivatives such as a compound having the structure of R ¹ and a leaving group X include commercially available alcohol compounds, or methanesulfonyl halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzenesulfonyl halide on the hydroxy group of the alcohol compound, Examples include alcohol derivatives obtained by reacting acetyl halide, acetic anhydride, trifluoroacetic anhydride, phosphorus oxychloride, phosphorus oxybromide, thionyl halide, sulfuryl halide, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like. Examples thereof include alcohols such as Fine Oxocol (registered trademark) 1600, 180, 180N, 180T, and 2000 manufactured by Nissan Chemical Industries, Ltd., or derivatives of the alcohol.

  Commercially available alcohols can be used as the alcohol having 2 to 8 allyl ether groups having the structure of A. For example, 2,3-diallyloxypropanol, 1,3-diallyloxy-2-propanol, 3,4-diallyloxybutanol, trimethylol methane diallyl ether, 1,1,1-trimethylol ethane diallyl ether, 1,1 1, 1-trimethylolpropane diallyl ether, ditrimethylolpropane triallyl ether, pentaerythritol triallyl ether, dipentaerythritol pentaallyl ether, and the like.

The intermediate (ene compound) is synthesized by reacting the carboxylic acid derivative with an alcohol derivative having two or more allyl ether groups. This method can use an existing condensation reaction. For example, using a catalyst such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine in a solvent such as dichloromethane, a temperature of room temperature (approximately 23 ° C.) to 110 ° C., 0 Performed in ~ 200 hours. The above reaction can also be carried out using a dicarboxylic acid compound as a raw material instead of an acid anhydride. In the case of a carboxylic acid that is difficult to dissolve in a solvent such as dichloromethane, a method of esterifying with an alcohol such as methanol, followed by a transesterification reaction with an alcohol compound, or a condensing agent such as carbodiimide The above intermediates (ene compounds) can also be synthesized by a method of reacting using a carboxylic acid or a method of converting a carboxylic acid to an acid chloride with thionyl chloride or the like and reacting with an alcohol compound.
Next, this ene compound can be oxidized with a peroxide to obtain an epoxy compound. Here, as the peroxide, for example, metachloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid, or the like can be used. This reaction can be carried out in a solvent such as chloroform at 0 to 60 ° C. for 1 to 200 hours. Moreover, it can also oxidize by the method as described in Unexamined-Japanese-Patent No. 2012-25688.

式［２］中、Ｒ^１乃至Ｒ^４、Ｌ、Ａ及びｎは前記と同じ意味を表す。The intermediate (ene compound) obtained by the above reaction can be exemplified by the formula [2].

In formula [2], R ^{1 to} R ⁴ , L, A and n represent the same meaning as described above.

[Curable composition]
Moreover, this invention is a curable composition containing the (a) epoxy compound represented by the said Formula [1], and the (b) hardening | curing agent.
Furthermore, the present invention is a curable composition comprising (a) an epoxy compound represented by the above formula [1] and (c) a curing catalyst.
Moreover, since the epoxy compound of this invention can react with the acid or base which arises from a general purpose hardening | curing agent or a curing catalyst, it can also be mix | blended with a general purpose epoxy resin composition.
The curable composition of the present invention may contain a curing agent and a curing catalyst, and may further contain a solvent, another epoxy compound, a surfactant, an adhesion promoter, and the like as necessary.

The ratio of the solid content in the curable composition of this invention can be 1-100 mass%, 5-100 mass%, 50-100 mass%, or 80-100 mass%.
Solid content is the ratio of the remaining component which removed the solvent from the curable composition.
In the present invention, since a liquid epoxy compound is used and a curing agent or a curing catalyst is mixed therewith, it is basically unnecessary to use a solvent, but it is possible to add a solvent if necessary. For example, the curing catalyst is solid, and the curing catalyst can be dissolved in a solvent such as propylene carbonate and mixed with a liquid epoxy compound to produce a curable compound. Even when the curing catalyst is dissolved in the liquid epoxy compound, a general solvent can be added to adjust the viscosity of the resulting curable composition.

[(A) Epoxy compound]
In the present invention, the epoxy compound represented by the above formula [1] and other epoxy compounds can be used in combination. The epoxy compound represented by the above formula [1] and the other epoxy compounds can be used in a molar ratio of epoxy groups in the range of 1: 0 to 1:20.
As an epoxy compound other than the epoxy compound represented by the formula [1], various polyfunctional epoxy compounds that are commercially available can be used without any particular limitation.

Examples of the epoxy compound that can be used in the present invention include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, Trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diglycerol polydiglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris (4-glycidyloxyphenyl) propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester 4,4′-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexanecarboxylic acid 3 ′, 4′-epoxycyclohexylmethyl, triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, Tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, pentaerythritol diglycidyl ether , Pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, phthalate digg Sidyl, diglycidyl tetrahydrophthalate, neopentyl glycol diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, triglycidyl isocyanurate, tris- (3,4-epoxybutyl) isocyanurate, tris- (4,5-epoxypentyl) Isocyanurate, tris- (5,6-epoxyhexyl) isocyanurate, tris- (7,8-epoxyoctyl) isocyanurate, tris (2-glycidyloxyethyl) isocyanurate, monoallyl diglycidyl isocyanurate, N, N '-Diglycidyl N ″-(2,3-dipropionyloxypropyl) isocyanurate, N, N′-bis (2,3-dipropionyloxypropyl) N ″ -glycidyl isocyanurate, tris (2, 2-bis (glycidyloxymethyl) butyl) 3,3 ′, 3 ″-(2,4,6-trioxo-1,3,5-triazine-1,3,5-triyl) tripropanoate, sorbitol poly Glycidyl ether, diglycidyl adipate, diglycidyl o-phthalate, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perfluorohexane diglycidyl ether, 4- (spiro [3 4-epoxycyclohexane-1,5 ′-[1,3] dioxane] -2′-yl) -1,2-epoxycyclohexane, 1,2-bis (3,4-epoxycyclohexylmethoxy) ethane, 4,5 -Epoxy-2-methylcyclohexanecarboxylic acid 4 ', 5'-epoxy-2'-methylcyclohexylmethyl, ethylene Recall bis (3,4-epoxycyclohexane carboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxy cyclopentyl) but ether, and the like, but is not limited thereto.
These epoxy compounds can be used alone or as a mixture of two or more.

In addition, the following commercial item can be mentioned as an example of the said epoxy compound.
Examples of the solid epoxy compound include TEPIC (registered trademark) -G, S, L, and HP [all manufactured by Nissan Chemical Industries, Ltd.].
In addition, as the liquid epoxy compound, TEPIC (registered trademark) -PAS B22, PAS B26, PAS B26L, VL, UC, FL [all manufactured by Nissan Chemical Industries, Ltd.], jER (registered trademark) 828, YX8000 [all manufactured by Mitsubishi Chemical Corporation], Rica Resin (registered trademark) DME100 [manufactured by Shin Nippon Rika Co., Ltd.], Celoxide 2021P [manufactured by Daicel Corporation], and the like.

[(B) Curing agent]
In the present invention, a curable composition containing (a) an epoxy compound represented by the above formula [1] and (b) a curing agent can be obtained.

As the curing agent, acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, or polymercaptans can be used. Among these, acid anhydrides and amines are particularly preferable. Even if these hardening | curing agents are solid, they can be used by melt | dissolving in a solvent. However, since the evaporation of the solvent causes a decrease in density of the cured product and a decrease in strength and a decrease in water resistance due to the formation of pores, the curing agent itself is preferably liquid at normal temperature and normal pressure.
A hardening | curing agent can be contained in the ratio of 0.5-1.5 equivalent with respect to 1 equivalent of epoxy groups of an epoxy compound, Preferably it is 0.8-1.2 equivalent. The equivalent of the curing agent to the epoxy compound is represented by an equivalent ratio of the curable group of the curing agent to the epoxy group. In addition, when using together the epoxy compound represented by the said Formula [1], and another epoxy compound, the equivalent with respect to the epoxy group of these all epoxy compounds becomes the said range.

The acid anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule. These acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trislimitate, maleic anhydride, tetrahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride Methylcyclohexene dicarboxylic acid anhydride, chlorendic acid anhydride, and the like.
Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride (methylnadic acid anhydride, methylhymic anhydride), hydrogenated methylnadicic acid which is liquid at normal temperature and normal pressure Preference is given to anhydrides, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride. These liquid acid anhydrides have a viscosity of about 10 to 1,000 mPa · s as measured at 25 ° C. In an acid anhydride group, one acid anhydride group is calculated as one equivalent.

  Examples of amines include piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, diethylenetriamine, and triethylenetetramine. Tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, menthanediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, Xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like can be mentioned. Among these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, bis (1-methyl-2-aminocyclohexyl) methane, menthanediamine, isophoronediamine, diaminodicyclohexylmethane Etc. can be preferably used.

  Examples of the phenol resin include phenol novolac resin and cresol novolac resin.

  The polyamide resin is produced by condensation of dimer acid and polyamine, and is a polyamide amine having a primary amine and a secondary amine in the molecule.

  Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, epoxy imidazole adduct, and the like.

  The polymercaptan is, for example, one having a mercaptan group at the end of a polypropylene glycol chain or one having a mercaptan group at the end of a polyethylene glycol chain, and preferably in liquid form.

Moreover, when obtaining hardened | cured material from the curable composition of this invention, a hardening accelerator (it is also mentioned a hardening adjuvant) may be used together suitably.
Curing accelerators include organophosphorus compounds such as triphenylphosphine and tributylphosphine; quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and tetrabutylphosphonium O, O-diethylphosphorodithioate; 1,8-diazabicyclo [ 5.4.0] Undec-7-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene and octylic acid, quaternary ammonium such as zinc octylate, tetrabutylammonium bromide Examples include salt. Other examples include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and amines such as 2,4,6-tris (dimethylaminomethyl) phenol and benzyldimethylamine, which are mentioned as the curing agents. It can be used as a curing accelerator for these types of curing agents.
These curing accelerators can be used at a ratio of 0.001 to 0.1 parts by mass with respect to 1 part by mass of the curing agent.

In this invention, a curable composition is obtained by mixing the epoxy compound represented by the said Formula [1], the said hardening | curing agent, and a hardening accelerator depending on necessity. The mixing is not particularly limited as long as it can be uniformly mixed, but can be performed using, for example, a reaction flask and a stirring blade or a mixer.
Mixing is performed under heating as necessary in consideration of the viscosity, and is performed at a temperature of 10 to 100 ° C. for 0.5 to 1 hour.
The obtained curable composition has an appropriate viscosity for use as a liquid sealing material. The curable composition of the present invention can be adjusted to an arbitrary viscosity, and is partially used in a transparent sealing material such as an LED by a casting method, a potting method, a dispenser method, a printing method, etc. Can be sealed. The curable composition is directly mounted in an LED or the like in a liquid state by the above-described method, and then dried and cured to obtain a cured epoxy resin.
The cured product obtained from the curable composition is pre-cured at a temperature of 100 to 120 ° C. by applying the curable composition to a substrate or pouring it onto a casting plate coated with a release agent, and 120 to 120- It is obtained by carrying out main curing (post-curing) at a temperature of 200 ° C.
The heating time is 1 to 12 hours, for example, about 2 to 5 hours for both preliminary curing and main curing.
The thickness of the coating film obtained from the curable composition of the present invention can be selected from the range of about 0.01 μm to 10 mm depending on the use of the cured product.

[(C) Curing catalyst]
In the present invention, a curable composition containing (a) an epoxy compound represented by the above formula [1] and (c) a curing catalyst can be obtained. The curing catalyst comprises (c1) an acid generator and / or (c2) a base generator. Thereby, even if the epoxy compound of the present invention and the curing catalyst are mixed, curing does not occur immediately, so that the storage stability is excellent and sufficient working time is obtained.

<(C1) Acid generator>
(C1) As the acid generator, a photoacid generator or a thermal acid generator can be used. The photo acid generator or thermal acid generator is not particularly limited as long as it generates an acid (Lewis acid or Bronsted acid) directly or indirectly by light irradiation or heating. The curable composition containing the thermal acid generator can be cured in a short time by heating. Moreover, since the curable composition which mix | blended the photo-acid generator hardens | cures by light irradiation irrespective of a heating, it can be used for a board | substrate and site | part with low heat resistance.

  Specific examples of the photoacid generator include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, selenium salts, metallocene complex compounds, iron arene complex compounds, disulfone compounds, sulfonic acid derivative compounds, triazine compounds, acetophenone derivatives. Compounds, diazomethane compounds, and the like.

  Examples of the iodonium salt include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-di-tert-butyldiphenyliodonium, 4-methylphenyl (4- ( 2-methylpropyl) phenyl) iodonium, 3,3′-dinitrophenyliodonium, 4- (1-ethoxycarbonylethoxy) phenyl (2,4,6-trimethylphenyl) iodonium, 4-methoxyphenyl (phenyl) iodonium, etc. Iodonium chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroarsene Diaryliodonium salts such as hexafluoroantimonate, and the like.

  Examples of the sulfonium salt include triphenylsulfonium, diphenyl (4-tert-butylphenyl) sulfonium, tris (4-tert-butylphenyl) sulfonium, diphenyl (4-methoxyphenyl) sulfonium, tris (4-methylphenyl). Sulfonium such as sulfonium, tris (4-methoxyphenyl) sulfonium, tris (4-ethoxyphenyl) sulfonium, diphenyl (4- (phenylthio) phenyl) sulfonium, tris (4- (phenylthio) phenyl) sulfonium, chloride, bromide, Triarylsulfonium salts such as trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate And the like.

  Examples of the phosphonium salt include chloride, bromide, and tetrafluoro of phosphonium such as tetraphenylphosphonium, ethyltriphenylphosphonium, tetra (p-methoxyphenyl) phosphonium, ethyltri (p-methoxyphenyl) phosphonium, and benzyltriphenylphosphonium. Examples thereof include arylphosphonium salts such as borate, hexafluorophosphate, and hexafluoroantimonate.

  Examples of the selenium salt include triaryl selenium salts such as triphenyl selenium hexafluorophosphate.

Examples of the iron arene complex compound include bis (η ⁵ -cyclopentadienyl) (η ⁶ -isopropylbenzene) iron (II) hexafluorophosphate.

  These photoacid generators can be used alone or in combination of two or more.

Examples of the thermal acid generator include sulfonium salts and phosphonium salts, and sulfonium salts are preferably used.
Examples of these exemplary compounds include the compounds mentioned as examples of various onium salts in the above-mentioned photoacid generator.
These thermal acid generators can be used alone or in combination of two or more.

Among these, as the acid generator (c1), a sulfonium salt compound or an iodonium salt compound is preferable. For example, a compound having an anionic species such as hexafluorophosphate or hexafluoroantimonate showing strong acidity is preferable.
The content of the (c1) acid generator in the curable composition of the present invention is preferably 0.1 to 20 parts by mass, or more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the (a) epoxy compound. May be 0.5 to 10 parts by mass. In addition, when using together the epoxy compound represented by the said Formula [1], and another epoxy compound, content with respect to 100 mass parts of all those epoxy compounds becomes the said range.

<(C2) Base generator>
(C2) As the base generator, a photobase generator or a thermal base generator can be used. The photobase acid generator or the heat base generator is not particularly limited as long as it generates a base (Lewis base or Bronsted base) directly or indirectly by light irradiation or heating. The curable composition containing the thermal base generator can be cured in a short time by heating. Moreover, since the curable composition which mix | blended the photobase generator hardens | cures by light irradiation irrespective of a heating, it can be used for a board | substrate and a site | part with low heat resistance.

Examples of the photobase generator include alkylamine photobase generators such as 9-anthrylmethyl = N, N-diethylcarbamate; 9-anthryl = N, N-dicyclohexylcarbamate, 1- (9,10-anthraquinone) 2-yl) ethyl = N, N-dicyclohexylcarbamate, dicyclohexylammonium = 2- (3-benzoylphenyl) propionate, 9-anthryl = N-cyclohexylcarbamate, 1- (9,10-anthraquinone-2-yl) ethyl = N-cyclohexyl carbamate, cyclohexyl ammonium = 2- (3-benzoylphenyl) propionate, (E) -N-cyclohexyl-3- (2-hydroxyphenyl) acrylamide and other cycloalkylamine photobase generators; 9-anthrylmethyl = Piperidine-1-carboxylate, (E) -1-piperidino-3- (2-hydroxyphenyl) -2-propen-1-one, (2-nitrophenyl) methyl = 4-hydroxypiperidine-1-carboxylate Piperidine photobase generators such as (2-nitrophenyl) methyl = 4- (methacryloyloxy) piperidine-1-carboxylate; guanidinium = 2- (3-benzoylphenyl) propionate, 1,2-diisopropyl-3- (Bis (dimethylamino) methylene) guanidinium = 2- (3-benzoylphenyl) propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium = n-butyltriphenylborate, 1, 5,7-triazabicyclo [4.4.0] dec-5-enium = -Guanidine photobase generators such as (9-oxoxanthen-2-yl) propionate; Imidazole photobase generators such as 1- (9,10-anthraquinone-2-yl) ethyl = imidazole-1-carboxylate Etc.
These photobase generators can be used singly or in combination of two or more.
The photobase generator is available as a commercial product. For example, the photobase generator WPBG series (WPBG-018, 027, 082, 140, 266, manufactured by Wako Pure Chemical Industries, Ltd.) 300) and the like can be preferably used.

Examples of the thermal base generator include carbamates such as 1-methyl-1- (4-biphenylyl) ethyl carbamate and 2-cyano-1,1-dimethylethyl carbamate; urea, N, N-dimethyl-N′— Ureas such as methylurea; guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate and guanidine phenylpropiolate; dihydropyridines such as 1,4-dihydronicotinamide; N- (isopropoxycarbonyl) -2,6-dimethyl Dimethylpiperidines such as piperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine; tetramethylammonium phenylsulfonylacetate, tetramethylphenylpropiolate Ann And quaternized ammonium salts such as monium; dicyandiamide and the like. U-CAT (registered trademark) SA810, SA831, SA841, SA851 [above, San Apro (strain), which is a salt of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) ) Made] and the like.
These thermal base generators can be used singly or in combination of two or more.

  The content of the (c2) base generator in the curable composition of the present invention is 0.1 to 20 parts by mass, or more preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass of the (a) epoxy compound. May be 0.5 to 10 parts by mass. In addition, when using together the epoxy compound represented by the said Formula [1], and another epoxy compound, content with respect to 100 mass parts of all those epoxy compounds becomes the said range.

  In the present invention, a curable composition is obtained by mixing the epoxy compound represented by the formula [1] and the curing catalyst. The operating conditions for mixing to obtain the curable composition are as described above.

In the present invention, a curable composition containing the epoxy compound represented by the above formula [1] and a photoacid generator or a photobase generator can be applied on a substrate and cured by light irradiation. Moreover, it can also heat before and after light irradiation.
Moreover, in this invention, the curable composition containing the epoxy compound represented by the said Formula [1] and a thermal acid generator or a thermal base generator can be apply | coated on a board | substrate, and it can harden | cure by heating.
Furthermore, a curable composition containing the epoxy compound represented by the above formula [1] and a thermal acid generator and a photoacid generator or a thermal base generator and a photobase generator is applied onto a substrate, and light irradiation is performed after heating. Can be cured.
Said curable composition can contain a solvent. The solvent described later can be used as the solvent.

  Examples of the method for applying the curable composition of the present invention on a substrate include a flow coating method, a spin coating method, a spray coating method, a screen printing method, a flexographic printing method, an ink jet printing method, a casting method, a bar coating method, Examples include curtain coating, roll coating, gravure coating, dipping, and slitting.

  The thickness of the coating film formed from the curable composition of the present invention can be selected from a range of about 0.01 μm to 10 mm depending on the use of the cured product. For example, when used for a photoresist, 0.05 to 10 μm. (Especially 0.1 to 5 μm), about 10 μm to 5 mm (especially 100 μm to 1 mm) when used for a printed wiring board, and 0.1 to 100 μm (when used for an optical thin film) In particular, it can be about 0.3 to 50 μm.

Examples of light to be irradiated or exposed in the case of using a photoacid generator or a photobase generator include gamma rays, X-rays, ultraviolet rays, and visible rays, and usually visible rays or ultraviolet rays, particularly ultraviolet rays are used. There are many cases.
The wavelength of light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, more preferably about 200 to 400 nm, and particularly about 300 to 400 nm.
The amount of irradiation light varies depending on the thickness of the coating film, but may be, for example, about ² to 20,000 mJ / cm ² , preferably about 5 to 5,000 mJ / cm ² .
The light source can be selected according to the type of light to be exposed. For example, in the case of ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deuterium lamp, a halogen lamp, laser light (helium-cadmium laser, excimer) Laser, etc.), UV-LED, etc. can be used. By such light irradiation, the curing reaction of the composition proceeds.

  In the case of using a thermal acid generator or a thermal base generator, heating of the coating film performed as necessary after light irradiation using a photoacid generator or a photobase generator is, for example, about room temperature (about 23 ° C.) to about 250 ° C. Done in The heating time can be selected from a range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, about 5 seconds to 2 hours.

  Furthermore, when forming a pattern or an image (for example, when manufacturing a printed wiring board etc.), you may pattern-expose the coating film formed on the base material. This pattern exposure may be performed by scanning with a laser beam or by irradiating light through a photomask. A pattern or an image can be formed by developing (or dissolving) a non-irradiated region (unexposed portion) generated by such pattern exposure with a developer.

As the developer, an alkaline aqueous solution or an organic solvent can be used.
Examples of the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate; quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Aqueous solution: An aqueous amine solution such as ethanolamine, propylamine, and ethylenediamine can be used.

  The alkaline developer is generally an aqueous solution of 10% by mass or less, preferably an aqueous solution of 0.1 to 3% by mass. Furthermore, alcohols and surfactants may be added to the developer and used, and the addition amount thereof is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the developer. Specifically, a 0.1-2.38 mass% tetramethylammonium hydroxide aqueous solution or the like can be used.

Moreover, the organic solvent as a developing solution can use a common organic solvent, for example, aromatic hydrocarbons, such as toluene; ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Esters such as ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; Amides such as N, N-dimethylformamide (DMF); Nitriles such as acetonitrile; Ketones such as acetone and cyclohexanone; Methanol, Ethanol, 2-propanol, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol And alcohols such as chromatography mono butyl ether. These can be used alone or as a mixture of two or more.
Of these, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and the like can be preferably used.

[solvent]
The above-mentioned curable composition can contain a solvent if necessary.
Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, and ethyl lactate Propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy- Hydroxy esters such as ethyl 2-methylpropionate and methyl 2-hydroxy-3-methylbutanoate; methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxy Propyl acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl acetate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxypropionic acid Methyl, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Propyl toxipropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxy Ethyl propionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, methyl cellosolve acetate, Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Ether esters such as butyl acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate; methyl ethyl ketone ( MEK), ketones such as 4-hydroxy-4-methyl-2-pentanone and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), propylene Glycol monoethyl ether, propylene Recall monopropyl ether, alcohols such as propylene glycol monobutyl ether; tetrahydrofuran (THF), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like ethers such as diethylene glycol ethyl methyl ether.

[Other curable monomers]
In the present invention, a vinyl group-containing compound, an oxetanyl group-containing compound, or the like can be used as the cationic curable monomer for the purpose of adjusting the viscosity of the curable composition or improving the curability.

The vinyl group-containing compound is not particularly limited as long as it is a compound having a vinyl group. For example, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), triethylene glycol And vinyl ether compounds such as divinyl ether. Also, a vinyl compound having a substituent such as an alkyl group or an allyl group at the α-position and / or β-position can be used. Moreover, the vinyl ether compound containing cyclic ether groups, such as an epoxy group and / or an oxetanyl group, can be used, for example, oxynorbornene divinyl ether, 3, 3- dimethanol oxetane divinyl ether, etc. are mentioned.
Moreover, the compound which has a vinyl group and a (meth) acryl group can be used, For example, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl etc. are mentioned.
These vinyl group-containing compounds can be used alone or in combination of two or more.

The oxetanyl group-containing compound is not particularly limited as long as it is a compound having an oxetanyl group, and 3-ethyl-3- (hydroxymethyl) oxetane (OXA), 3-ethyl-3- (phenoxymethyl) oxetane (POX), Bis ((3-ethyl-3-oxetanyl) methyl) ether (DOX), 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene (XDO), 3-ethyl-3- ( 2-ethylhexyloxymethyl) oxetane (EHOX), 3-ethyl-3-((3-triethoxysilylpropoxy) methyl) oxetane (TESOX), oxetanylsilsesquioxane (OX-SQ), phenol novolac oxetane (PNOX- 1009) and the like.
A compound having an oxetanyl group and a (meth) acryl group can be used, and examples thereof include (3-ethyl-3-oxetanyl) methyl (meth) acrylate.
These oxetanyl group-containing compounds can be used alone or in combination of two or more.

[Other ingredients]
The above composition may contain a conventional additive as required. Examples of such additives include pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistances). Stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, fillers, antistatic agents, curing agents and the like. These additives may be used alone or in combination of two or more.

A surfactant may be added to the curable composition of the present invention for the purpose of improving coatability. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants, but are not particularly limited thereto. The said surfactant can be used individually or in combination of 2 or more types.
Among these surfactants, a fluorosurfactant is preferable because of its high coating property improving effect. Specific examples of the fluorosurfactant include, for example, EFTOP (registered trademark) EF-301, EF-303, and EF-352 [all manufactured by Mitsubishi Materials & Chemicals Co., Ltd.], MegaFuck (registered trademark) ) F-171, F-173, F-482, R-08, R-30, R-90, BL-90 [all manufactured by DIC Corporation], Florard FC-430, FC-431 [all manufactured by 3M Japan Co., Ltd.], Asahi Guard (registered trademark) AG-710 (manufactured by Asahi Glass Co., Ltd.), Surflon S-382, SC-101, SC-102, SC-103 SC-104, SC-105, SC-106 [all manufactured by AGC Seimi Chemical Co., Ltd.] and the like, but are not limited thereto.
The addition amount of the surfactant in the curable composition of the present invention is 0.01 to 5% by mass, preferably 0.01 to 3% by mass, based on the solid content of the curable composition. Preferably it is 0.01-2 mass%.

An adhesion promoter can be added to the curable composition of the present invention for the purpose of improving the adhesion to the substrate after development. Examples of these adhesion promoters include chlorosilanes such as chlorotrimethylsilane, trichloro (vinyl) silane, chloro (dimethyl) (vinyl) silane, chloro (methyl) (diphenyl) silane, and chloro (chloromethyl) (dimethyl) silane. Methoxytrimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, ethoxy (dimethyl) (vinyl) silane, dimethoxydiphenylsilane, triethoxy (phenyl) silane, 3-chloropropyltrimethoxysilane, 3-aminopropyltriethoxysilane, Alkoxysilanes such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, trimethoxy (3- (N-piperidinyl) propyl) silane; Silazanes such as Rudisilazane, N, N′-bis (trimethylsilyl) urea, dimethyl (trimethylsilyl) amine, trimethylsilylimidazole; imidazole, indazole, benzimidazole, benzotriazole, mercaptoimidazole, mercaptopyrimidine 2-mercaptobenzimidazole, 2-mercapto Examples thereof include nitrogen-containing heterocyclic compounds such as benzoxazole, 2-mercaptobenzothiazole, urazole and thiouracil; ureas such as 1,1-dimethylurea and 1,3-dimethylurea, and thioureas. These adhesion promoters can be used alone or in combination of two or more.
The addition amount of the adhesion promoter in the curable composition of the present invention is usually 20% by mass or less, preferably 0.01 to 10% by mass, more preferably based on the solid content of the curable composition. 0.05-5 mass%.

The curable composition of the present invention may contain a sensitizer. Examples of sensitizers that can be used include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Further, as sensitizing dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes And pyrylium salt pigments. Particularly preferred is an anthracene-based sensitizer, and when used in combination with a cationic curing catalyst (radiation sensitive cationic polymerization initiator), the sensitivity is drastically improved and also has a radical polymerization initiation function. For example, in the case of adopting a hybrid type that uses a cationic curing system and a radical curing system in combination, the catalyst species can be simplified. As specific anthracene compounds, dibutoxyanthracene, dipropoxyanthraquinone and the like are effective.
Examples of the sensitizer when using a base generator as a curing catalyst include acetophenones, benzoins, benzophenones, anthraquinones, xanthones, thioxanthones, ketals, and tertiary amines. it can.
The addition amount of the sensitizer in the curable composition of the present invention is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content of the curable composition. .

  The curable composition containing the polyfunctional epoxy compound of the present invention and a curing agent or a curing catalyst has light and thermosetting properties, and has a high refractive index of an adhesive and an antireflection film (such as an antireflection film for a liquid crystal display). It can be widely used in the field of electronic materials such as layers, optical thin films (reflecting plates, etc.), encapsulants for electronic parts, printed wiring boards, interlayer insulating film materials (interlayer insulating film materials for build-up printed boards, etc.). In particular, it can be widely used as an electronic material that is required to have a low dielectric constant, such as a printed wiring board and an interlayer insulating film material.

  The polyfunctional epoxy compound of the present invention and the curable composition containing the same are a semiconductor sealing material, a transparent sealing agent, an adhesive for electronic materials, an optical adhesive, a printed wiring board material, an interlayer insulating film material, and fiber reinforcement. Plastic, Stereolithography ink, Paint ink, Water repellent coating material, Water slidable coating material, Lipophilic coating material, Self-healing material, Biocompatible material, Birefringence control material, Pigment dispersant, Filler dispersant, Rubber It can be suitably used as a main agent, a crosslinking agent, a diluent, a leveling agent, and a compatibilizing agent for various materials such as a modifier.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) ¹ H NMR spectrum apparatus: JNM-ECX300 manufactured by JEOL RESONANCE
Standard: Tetramethylsilane (0.00ppm)
(2) GC-MS (gas chromatograph mass spectrometry)
Equipment: GCMS-QP2010 Ultra manufactured by Shimadzu Corporation
Column: Agilent Technology Co., Ltd. Agilent J & W GC column HP-5 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm)
Injection volume: 2.0 μL
Inlet temperature: 250 ° C
Column temperature: 40 ° C. (5 minutes), 20 ° C./min to 300 ° C., 300 ° C. (12 minutes)
(3) Viscosity Equipment: TVE-22L, TVE-25H manufactured by Toki Sangyo Co., Ltd.
(4) Melting point Apparatus: Rigaku Corporation Thermo plus EVO / TG-DTA TG8120
(5) Epoxy equivalent apparatus: Kyoto Denshi Kogyo Co., Ltd. potentiometric automatic titrator AT-510
(6) Flexural modulus, deflection Device: Desktop precision universal testing machine Autograph AGS-5kNX, manufactured by Shimadzu Corporation
(7) Relative permittivity Equipment: E4980A Precision LCR meter, manufactured by Keysight Technologies, Inc. Sample holder: 12962 room temperature sample holder, manufactured by Toyo Technica Co., Ltd. (8) Contact angle Equipment: Automatic contact angle meter, manufactured by Kyowa Interface Science Co., Ltd. DM-301
Measurement temperature: 23 ° C
(9) Oven device: Yamato Kagaku Co., Ltd. blown low temperature thermostat DNF400
(10) Stirring and defoaming device: Rotating / revolving mixer manufactured by Shinkey Co., Ltd. Nertaro Awatori (registered trademark) ARE-310
(11) Spin coater: Mikasa Co., Ltd. spin coater 1H-D7
(12) UV curing apparatus: US5-0201 manufactured by Eye Graphics Co., Ltd.
Lamp: H02-L41 made by Eye Graphics Co., Ltd.

Abbreviations represent the following meanings.
EHA: 2-ethylhexanoic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
IAA: 5,9-dimethyl-2- (1,5-dimethylhexyl) decanoic acid [Fine oxocol (registered trademark) isoarachidic acid manufactured by Nissan Chemical Industries, Ltd.]
IPA: 2-hexyldecanoic acid [Fine oxocol (registered trademark) isopalmitic acid manufactured by Nissan Chemical Industries, Ltd.]
ISA: 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid [Fine oxocol (registered trademark) isostearic acid manufactured by Nissan Chemical Industries, Ltd.]
ISAN: 8-Methyl-2- (4-methylhexyl) decanoic acid [Fine oxocol (registered trademark) isostearic acid N manufactured by Nissan Chemical Industries, Ltd.]
STA: Stearic acid [Lunac (registered trademark) S-98 manufactured by Kao Corporation]
TMPDA: trimethylolpropane diallyl ether [manufactured by Aldrich, purity 90%]
PETTA: pentaerythritol triallyl ether [manufactured by Aldrich, purity 70%]
DMAP: 4-dimethylaminopyridine [manufactured by Wako Pure Chemical Industries, Ltd.]
EDC: 1-ethyl-3- (3- (dimethylamino) propyl) carbodiimide hydrochloride [manufactured by Wako Pure Chemical Industries, Ltd.]
mCPBA: m-chloroperbenzoic acid [manufactured by Wako Pure Chemical Industries, Ltd., purity 70%]
BPA: bisphenol A type epoxy resin [jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation]
HBPA: hydrogenated bisphenol A type epoxy resin [jER (registered trademark) YX8000 manufactured by Mitsubishi Chemical Corporation]
CEL: 3,4-epoxycyclohexanecarboxylic acid (3,4-epoxycyclohexyl) methyl [Celoxide 2021P manufactured by Daicel Corporation]
TMPTG: Trimethylolpropane triglycidyl ether [Denacol EX-321 manufactured by Nagase ChemteX Corporation]
TEPIC: Triglycidyl isocyanurate [TEPIC (registered trademark) -S manufactured by Nissan Chemical Industries, Ltd.]
DOX: Bis ((3-ethyl-3-oxetanyl) methyl) ether [Aron Oxetane (registered trademark) OXT-221 manufactured by Toagosei Co., Ltd.]
MH700: 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture (molar ratio 70:30) [Rikacid (registered trademark) MH-700 manufactured by Shin Nippon Rika Co., Ltd.]
PX4ET: Tetrabutylphosphonium O, O-diethyl phosphorodithioate [Hishikorin (registered trademark) PX-4ET manufactured by Nippon Chemical Industry Co., Ltd.]
C101A: Diphenyl (4- (phenylthio) phenyl) sulfonium hexafluoroantimonate (V) / propylene carbonate solution [CPI (registered trademark) -101A manufactured by San Apro Co., Ltd.]
CDMS: Cyclic dimethyl silicone oil [Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone (registered trademark) KF-995]
DMS: dimethyl silicone oil [Shin-Etsu Silicone (registered trademark) KF-968, manufactured by Shin-Etsu Chemical Co., Ltd.]
MPS: Methyl phenyl silicone oil [Shin-Etsu Silicone (registered trademark) KF-50, manufactured by Shin-Etsu Chemical Co., Ltd.]

[Example 1] Preparation of 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoate 2,2-bis (glycidyloxymethyl) butyl (ISA2G) 30.0 g (105 mmol), TMPDA 27.6 g (net 116 mmol) and dichloromethane 400 g were charged. To this solution, 16.1 g (132 mmol) of DMAP and 25.3 g (132 mmol) of EDC were added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 2 days. The reaction solution was washed with 1N hydrochloric acid and 5% by mass brine, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane: ethyl acetate = 95: 5 (volume ratio)) to give 2- (4,4-dimethylpentan-2-yl) -5,7,7- Thus, 34.1 g of 2,2-bis (allyloxymethyl) butyl trimethyloctanoate (ISA2A) was obtained as a colorless transparent liquid.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0-5.8 (m, 2H), 5.3-5.1 (m, 4H), 4.1-3.9 (m, 6H) , 3.4 to 3.2 (s, 4H), 2.2 to 0.8 (m, 40H)
GC-MS (CI): m / z = 481 (M + 1)

The reaction flask was charged with 33.8 g (70 mmol) of ISA2A and 740 g of chloroform. To this solution, 45.1 g (net 183 mmol) of mCPBA was added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 5 days. To this reaction solution, 300 mL of a 10% by mass aqueous sodium thiosulfate solution was added to decompose mCPBA. The organic layer was washed with a 5 mass% aqueous sodium bicarbonate solution and water, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (solvent gradient, hexane: ethyl acetate = 90: 10 to 80:20 (volume ratio)) to give the desired product 2- (4,4-dimethylpentane- 2-yl) -5,7,7-trimethyloctanoic acid 2,2-bis (glycidyloxymethyl) butyl (ISA2G) 12.8 g was obtained as a colorless transparent liquid. The viscosity of the obtained ISA2G was 345 mPa · s (25 ° C.), and the epoxy equivalent measured according to JIS K7236: 2009 was 259.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 4.0 (m, 2H), 3.7 (m, 2H), 3.5 to 3.3 (m, 6H), 3.1 (m, 2H) ), 2.8 (m, 2H), 2.6 (m, 2H), 1.8 to 0.8 (m, 40H)
GC-MS (CI): m / z = 513 (M + 1)

[Example 2] Preparation of 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid 3-glycidyloxy-2,2-bis (glycidyloxymethyl) propyl (ISA3G) A reaction flask was charged with 50.0 g PETTA (net 137 mmol) and 660 g dichloromethane. To this solution, 41.5 g (146 mmol) of ISA, 21.4 g (175 mmol) of DMAP and 33.5 g (175 mmol) of EDC were added with stirring, and the mixture was stirred overnight (about 16 hours) at room temperature (about 23 ° C.). The reaction solution was washed with a 5 mass% aqueous sodium bicarbonate solution, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (solvent gradient, hexane: ethyl acetate = 99: 1 to 95: 5 (volume ratio)) to give 2- (4,4-dimethylpentan-2-yl) 40.0 g of -5,7,7-trimethyloctanoic acid 3-allyloxy-2,2-bis (allyloxymethyl) propyl (ISA3A) was obtained as a colorless transparent liquid.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0 to 5.8 (m, 3H), 5.3 to 5.1 (m, 6H), 4.2 to 4.0 (m, 2H) , 4.0 to 3.9 (m, 6H), 3.5 to 3.4 (s, 6H), 2.3 to 0.7 (m, 35H)
GC-MS (CI): m / z = 523 (M + 1)

The reaction flask was charged with 39.5 g (76 mmol) of ISA3A and 400 g of chloroform. To this solution, 67.0 g (net 272 mmol) of mCPBA was added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 5 days. To this reaction solution, 500 mL of a 10% by mass aqueous sodium thiosulfate solution was added to decompose mCPBA. The organic layer was washed with a 5 mass% aqueous sodium bicarbonate solution and water, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane: ethyl acetate = 90: 10 (volume ratio)) to give 2- (4,4-dimethylpentan-2-yl) -5, which is the target product. 3,1.9 g of 7,7-trimethyloctanoic acid 3-glycidyloxy-2,2-bis (glycidyloxymethyl) propyl (ISA3G) was obtained as a colorless transparent liquid. The obtained ISA3G had a viscosity of 625 mPa · s (25 ° C.) and an epoxy equivalent of 189.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 4.2 to 4.0 (m, 2H), 3.8 to 3.6 (m, 3H), 3.6 to 3.4 (m, 6H) , 3.4 to 3.3 (m, 3H), 3.2 to 3.0 (m, 3H), 2.8 to 2.7 (m, 3H), 2.6 to 2.5 (m, 3H), 2.2 to 0.7 (m, 35H)
GC-MS (CI): m / z = 571 (M + 1)

[Example 3] Production of 2,2-bis (glycidyloxymethyl) butyl stearate (STA2G) A reaction flask was charged with 30.0 g (105 mmol) of STA, 27.1 g (net 114 mmol) of TMPDA and 400 g of dichloromethane. To this solution, 15.5 g (127 mmol) of DMAP and 24.3 g (127 mmol) of EDC were added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 3 days. The reaction solution was washed with 1N hydrochloric acid and 5% by mass brine, and then the solvent was distilled off. By purifying the obtained residue by silica gel chromatography (solvent gradient, hexane: ethyl acetate = 99: 1 to 95: 5 (volume ratio)), 2,2-bis (allyloxymethyl) butyl stearate ( (STA2A) 44.6 g was obtained as a white powder.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0-5.8 (m, 2H), 5.3-5.1 (m, 4H), 4.1-3.9 (m, 6H) 3.4-3.3 (s, 4H), 2.4-2.2 (m, 2H), 1.8-0.8 (m, 38H)
GC-MS (CI): m / z = 481 (M + 1)

The reaction flask was charged with 44.6 g (93 mmol) of the above STA2A and 740 g of chloroform. To this solution, 59.5 g (net 241 mmol) of mCPBA was added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 3 days. To this reaction solution, 300 mL of a 10% by mass aqueous sodium thiosulfate solution was added to decompose mCPBA. The organic layer was washed with a 5 mass% aqueous sodium bicarbonate solution, and then the solvent was distilled off. By purifying the obtained residue by silica gel chromatography (hexane: ethyl acetate = 85: 15 (volume ratio)), the desired product 2,2-bis (glycidyloxymethyl) butyl stearate (STA2G) 33 0.4 g was obtained as a white powder. The obtained STA2G had a melting point of 34 ° C. and an epoxy equivalent of 257.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 4.1 to 4.0 (m, 2H), 3.8 to 3.6 (m, 2H), 3.5 to 3.3 (m, 6H) , 3.2 to 3.0 (m, 2H), 2.8 to 2.7 (m, 2H), 2.7 to 2.5 (m, 2H), 2.4 to 2.2 (m, 2H), 1.9 to 0.8 (m, 38H)
GC-MS (CI): m / z = 513 (M + 1)

[Example 4] Production of 2,2-bis (glycidyloxymethyl) butyl 8-methyl-2- (4-methylhexyl) decanoate (ISAN2G) In a reaction flask, 30.0 g (105 mmol) of ISAN, TMPDA 27. 6 g (net 116 mmol) and 400 g of dichloromethane were charged. To this solution, 15.5 g (127 mmol) of DMAP and 24.3 g (127 mmol) of EDC were added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 30 hours. The reaction solution was washed with 1N hydrochloric acid and 5% by mass brine, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (solvent gradient, hexane: ethyl acetate = 99: 1 to 95: 5 (volume ratio)) to give 8-methyl-2- (4-methylhexyl) decanoic acid. 29.0 g of 2,2-bis (allyloxymethyl) butyl (ISA2A) was obtained as a colorless transparent liquid.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0-5.8 (m, 2H), 5.3-5.1 (m, 4H), 4.1-3.9 (m, 6H) 3.4 to 3.2 (s, 4H), 2.5 to 2.3 (m, 1H), 1.7 to 0.7 (m, 39H)
GC-MS (CI): m / z = 481 (M + 1)

Into the reaction flask, 28.9 g (60 mmol) of the above ISAN2A and 740 g of chloroform were charged. To this solution, 38.5 g (net 156 mmol) of mCPBA was added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 5 days. To this reaction solution, 300 mL of a 10% by mass aqueous sodium thiosulfate solution was added to decompose mCPBA. The organic layer was washed with 5% by mass aqueous sodium bicarbonate solution and 5% by mass brine, and then the solvent was distilled off. By purifying the obtained residue by silica gel chromatography (hexane: ethyl acetate = 95: 5 (volume ratio)), the desired product, 8-methyl-2- (4-methylhexyl) decanoic acid 2,2 -7.7 g of bis (glycidyloxymethyl) butyl (ISAN2G) was obtained as a colorless transparent liquid. The obtained ISAN2G had a viscosity of 114 mPa · s (25 ° C.) and an epoxy equivalent of 265.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 4.1-3.9 (m, 2H), 3.8-3.6 (m, 2H), 3.4-3.2 (m, 6H) , 3.2 to 3.0 (m, 2H), 2.8 to 2.7 (m, 2H), 2.6 to 2.5 (m, 2H), 2.5 to 0.6 (m, 40H)
GC-MS (CI): m / z = 513 (M + 1)

[Example 5] Production of 2,2-bis (glycidyloxymethyl) butyl 2-hexyldecanoate (IPA2G) A reaction flask was charged with 50.0 g (195 mmol) of IPA, 50.1 g (net 210 mmol) of TMPDA and 660 g of dichloromethane. It is. To this solution, 28.5 g (233 mmol) of DMAP and 44.9 g (234 mmol) of EDC were added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 2 days. The reaction solution was washed with 1N hydrochloric acid and 5% by mass brine, and then the solvent was distilled off. By purifying the obtained residue by silica gel chromatography (hexane: ethyl acetate = 95: 5 (volume ratio)), 56.0 g of 2,2-bis (allyloxymethyl) butyl 2-hexyldecanoate (IPA2A) Was obtained as a colorless transparent liquid.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0-5.8 (m, 2H), 5.3-5.2 (m, 2H), 5.2-5.1 (m, 2H) , 4.1-4.0 (s, 2H), 4.0-3.9 (m, 4H), 3.4-3.3 (s, 4H), 2.4-2.2 (m, 1H), 1.7 to 1.5 (m, 2H), 1.5 to 1.3 (4H), 1.3 to 1.2 (m, 20H), 1.0 to 0.8 (m, 9H)
GC-MS (CI): m / z = 453 (M + 1)

Into a reaction flask, 56.0 g (124 mmol) of the above IPA2A and 740 g of chloroform were charged. To this solution, 79.2 g (net 321 mmol) of mCPBA was added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 5 days. To this reaction solution, 300 mL of a 10% by mass aqueous sodium thiosulfate solution was added to decompose mCPBA. The organic layer was washed with a 5 mass% aqueous sodium bicarbonate solution and water, and then the solvent was distilled off. By purifying the obtained residue by silica gel chromatography (hexane: ethyl acetate = 75: 25 (volume ratio)), the target product, 2-hexyldecanoate 2,2-bis (glycidyloxymethyl) butyl (IPA2G) ) 45.7 g was obtained as a colorless transparent liquid. The obtained IPA2G had a viscosity of 61 mPa · s (25 ° C.) and an epoxy equivalent of 228.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 4.1 to 3.9 (m, 2H), 3.8 to 3.6 (m, 2H), 3.5 to 3.2 (m, 6H) , 3.2 to 3.0 (m, 2H), 2.8 to 2.7 (m, 2H), 2.6 to 2.5 (m, 2H), 2.5 to 0.7 (m, 36H)
GC-MS (CI): m / z = 541 (M + 1)

[Example 6] Preparation of 2,2-bis (glycidyloxymethyl) butyl (IAA2G) 5,9-dimethyl-2- (1,5-dimethylhexyl) decanoate In a reaction flask, 30.0 g (96 mmol) of ISA , TMPDA 25.1 g (net 105 mmol) and dichloromethane 400 g were charged. To this solution, 14.1 g (115 mmol) of DMAP and 22.1 g (115 mmol) of EDC were added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 2 days. The reaction solution was washed with 1N hydrochloric acid and 5% by mass brine, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (solvent gradient, hexane: ethyl acetate = 100: 0 to 95: 5 (volume ratio)) to obtain 5,9-dimethyl-2- (1,5-dimethyl). 24.3 g of hexyl) decanoic acid 2,2-bis (allyloxymethyl) butyl (IAA2A) was obtained as a colorless transparent liquid.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0 to 5.8 (m, 2H), 5.3 to 5.1 (m, 4H), 4.1 to 3.9 (m, 6H) , 3.4 to 3.3 (s, 4H), 2.5 to 0.7 (m, 44H)
GC-MS (CI): m / z = 509 (M + 1)

A reaction flask was charged with 24.2 g (48 mmol) of the above IAA2A and 740 g of chloroform. To this solution, 30.5 g (net 124 mmol) of mCPBA was added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 5 days. To this reaction solution, 300 mL of a 10% by mass aqueous sodium thiosulfate solution was added to decompose mCPBA. The organic layer was washed with 5% by mass aqueous sodium bicarbonate solution and 5% by mass brine, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (solvent gradient, hexane: ethyl acetate = 99: 1 to 95: 5 (volume ratio)), whereby 5,9-dimethyl-2- (1 , 5-dimethylhexyl) decanoic acid 2,2-bis (glycidyloxymethyl) butyl (IAA2G) 18.7 g was obtained as a colorless transparent liquid. The obtained IAA2G had a viscosity of 217 mPa · s (25 ° C.) and an epoxy equivalent of 295.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 4.1 to 3.9 (m, 2H), 3.8 to 3.6 (m, 2H), 3.5 to 3.2 (m, 6H) , 3.2 to 3.0 (m, 2H), 2.9 to 2.7 (m, 2H), 2.6 to 2.4 (m, 2H), 2.4 to 0.5 (m, 44H)
GC-MS (CI): m / z = 541 (M + 1)

[Example 7] Production of 2,2-bis (glycidyloxymethyl) butyl 2-ethylhexanoate (EHA2G) In a reaction flask, 30.0 g (210 mmol) of EHA, 53.5 g (net of 250 mmol) of TMPDA and 300 g of dichloromethane were added. Prepared. To this solution, 30.5 g (250 mmol) of DMAP and 47.9 g (250 mmol) of EDC were added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 2 days. The reaction solution was washed with 1N hydrochloric acid and 5% by mass brine, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (solvent gradient, hexane: ethyl acetate = 99: 1 to 95: 5 (volume ratio)) to give 2,2-bis (allyloxymethyl) -2-ethylhexanoate. ) 58.9 g of butyl (EHA2A) was obtained as a colorless transparent liquid.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 6.0 to 5.8 (m, 2H), 5.4 to 5.1 (m, 4H), 4.1 to 3.9 (m, 6H) , 3.4 to 3.2 (s, 4H), 2.4 to 2.2 (m, 1H), 1.8 to 1.2 (m, 10H), 1.0 to 0.8 (m, 9H)
GC-MS (CI): m / z = 341 (M + 1)

The reaction flask was charged with 58.8 g (170 mmol) of the above EHA2A and 500 g of chloroform. To this solution, 110.8 g (net 642 mmol) of mCPBA was added with stirring, and the mixture was stirred at room temperature (approximately 23 ° C.) for 5 days. To this reaction solution, 300 mL of a 10% by mass aqueous sodium thiosulfate solution was added to decompose mCPBA. The organic layer was washed with a 5 mass% aqueous sodium bicarbonate solution and water, and then the solvent was distilled off. By purifying the obtained residue by silica gel chromatography (hexane: ethyl acetate = 99: 1 (volume ratio)), 2-ethylhexanoate 2,2-bis (glycidyloxymethyl) butyl (the target product) 21.6 g of EHA2G) was obtained as a colorless transparent liquid. The obtained EHA2G had a viscosity of 170 mPa · s (25 ° C.) and an epoxy equivalent of 210.
¹ H NMR (300 MHz, CDCl ₃ ): δ = 4.0 (m, 2H), 3.7 (m, 2H), 3.5 to 3.3 (m, 6H), 3.1 (m, 2H) ), 2.8-2.7 (m, 2H), 2.6-2.5 (m, 2H), 2.4-2.2 (m, 1H), 1.7-1.4 (m , 6H), 1.4 to 1.2 (m, 4H), 1.0 to 0.8 (m, 9H)
GC-MS (CI): m / z = 373 (M + 1)

[Examples 8 to 10, Comparative Examples 1 to 3] Solubility in silicones ISA2G, ISA3G and STA2G obtained in Examples 1 to 3 and BPA, HBPA and CEL which are general-purpose epoxy compounds to various silicones Was evaluated for solubility.
Each epoxy compound was mixed with various silicones described in Table 1 so that the concentrations thereof were 10% by mass, 20% by mass, and 50% by mass. After stirring this for 5 minutes at room temperature (approximately 23 ° C.), the dissolved state was visually confirmed and evaluated according to the following criteria. The results are also shown in Table 1.
[Solubility Evaluation Criteria]
A: dissolved at all concentrations B: not dissolved at 50% by mass, but dissolved at 10% by mass and 20% by mass C: not dissolved at 20% by mass and 50% by mass, but at 10% by mass Dissolved D: Not dissolved at all concentrations

As shown in Table 1, the epoxy compound of the present invention was dissolved in 50% by mass with respect to CDMS (that is, the same mass with respect to CDMS) (Examples 8 to 10). Especially, ISA2G showed the solubility of 10 mass% or more with respect to various silicones (Example 8).
On the other hand, BPA, HBPA, and CEL, which are general-purpose epoxy compounds, did not dissolve in any silicone even at 10% by mass (Comparative Examples 1 to 3).
As described above, it was confirmed that the epoxy compound of the present invention has good solubility in silicone.

[Examples 11 to 16, Comparative Examples 4 to 6] Preparation of Cured Product 100 parts by mass of the epoxy compound described in Table 2, MH700 as a curing agent and an equimolar amount with the epoxy group of the epoxy compound, and PX4ET as a curing accelerator 1 part by weight was added. This mixture was degassed by stirring at room temperature (approximately 23 ° C.) for 30 minutes under reduced pressure to prepare curable compositions 1 to 9.
Each curable composition was sandwiched between two glass substrates that had been release-treated with Optool (registered trademark) DSX [manufactured by Daikin Industries, Ltd.] together with a 3 mm thick U-shaped silicone rubber spacer. This was heated in an oven at 100 ° C. for 2 hours (preliminary curing), then heated to 150 ° C. and heated for 5 hours (main curing). After slow cooling, the glass substrate was removed to obtain each cured product having a thickness of 3 mm.
About the obtained hardened | cured material, the water absorption rate, the bending elastic modulus, and bending were evaluated. Each physical property value was measured by the following procedure. The results are also shown in Table 2.

[Water absorption rate]
It measured according to JIS K-6911: 2006. Specifically, first, as a pretreatment, a test piece (30 × 30 × 3 mm) was dried for 24 hours in a glass container kept at 50 ° C. with an oil bath. This test piece was cooled to 20 ° C. in a desiccator, and its mass (W ₁ [g]) was measured. Next, the test piece was immersed in boiling distilled water for 100 hours and then taken out, cooled in running water at 20 ° C. for 30 minutes, wiped off moisture, and immediately subjected to mass (W ₂ [g]) after water absorption. Weighed. From these values, the water absorption was calculated by the following formula.
Water absorption [%] = (W ₂ −W ₁ ) ÷ W ₁ × 100

[Bending elastic modulus]
It measured according to JIS K-6911: 2006. Specifically, a load is applied with a pressure wedge to the center of a test piece (80 × 10 × 3 mm) supported at a distance between fulcrums of 64 mm, and the gradient F / Y [N / mm] of the linear portion of the load-deflection curve is set. Asked. From this and the values of the distance L [mm] between the fulcrums, the width W [mm] and the thickness h [mm] of the test piece, the bending elastic modulus was calculated by the following formula.
Flexural modulus [MPa] = (L ³ ÷ 4Wh ³ ) × (F / Y)

[Bending] Bending (pushing distance) at the breaking point. > 30 falls before breaking.

As shown in Table 2, the cured product obtained by using the epoxy compound of the present invention has a low water absorption of 0.5 to 1.8%, and the deflection is more than 30 mm, so that the flexibility is high. (Examples 11 to 16). In particular, the epoxy compound having a branched alkyl chain showed a water absorption of 1% or less (Examples 11, 12, 14 to 16).
On the other hand, BPA, CEL, and TMPTG, which are general-purpose epoxy compounds, all had small deflection and low flexibility (Comparative Examples 4 to 6). Furthermore, in CEL and TMPTG, the water absorption rate was as high as nearly 3%, and the result that it was easy to absorb water was obtained (Comparative Examples 5 and 6).

[Examples 17 to 21, Comparative Examples 7 and 8] Relative permittivity of cured products Curable compositions 1 to 3, 5, and 6 obtained in Examples 11 to 13, 15 and 16, and Comparative Examples 5 and 6 8 and 9, each cured product having a thickness of 0.5 mm was obtained in the same manner as in Example 11 except that the thickness of the spacer made of silicone rubber was changed to 0.5 mm.
About the obtained hardened | cured material, the dielectric constant was evaluated. The relative permittivity is measured by measuring the capacitance Cp when a voltage of 1 V and 1 MHz is applied to the test piece sandwiched between the electrodes of the holder, and dividing by the electrostatic capacitance C ₀ measured under the same conditions. Calculated. The results are also shown in Table 3.

  As shown in Table 3, the hardened | cured material obtained using the epoxy compound of this invention showed the low dielectric constant compared with the hardened | cured material obtained using CEL and TMPTG which are general purpose epoxy compounds ( Examples 17 to 21 and Comparative Examples 7 and 8). Among them, ISA2G showed a very low dielectric constant of 2.69 (Example 17).

[Examples 22 to 27, Comparative Examples 9 and 10] Production 2 of cured product
Each cured product having a thickness of 3 mm was obtained in the same manner as in Example 11 except that the types and amounts of the epoxy compounds described in Table 4 were used.
About the obtained hardened | cured material, the dielectric constant and the water absorption were evaluated by the method as described in Example 17 and Example 11. The results are also shown in Table 4.

  As shown in Table 4, it was confirmed that by adding the epoxy compound of the present invention to a general-purpose epoxy compound, the relative permittivity of the cured product can be reduced according to the amount added (Comparative Example 9 and Example 22). To 24, Comparative Example 10 and Examples 25 to 27). Moreover, when it added to the general purpose epoxy compound with a comparatively high water absorption, it was confirmed that the water absorption of the hardened | cured material can be reduced according to the addition amount (Comparative Example 10 and Examples 25-27).

[Examples 28 to 32, Comparative Examples 11 to 14] Contact angle of the cured product 2 parts by mass of C101A was added as a photoacid generator to the epoxy compound or cationic curable monomer of the type and amount shown in Table 5. This mixture was stirred and degassed (2,000 rpm, 10 minutes, further 1,000 rpm, 10 minutes) to prepare curable compositions 17 to 23.
Each curable composition was spin-coated (1,500 rpm, 30 seconds) on a glass substrate previously treated with UV ozone. The obtained coating film is exposed to UV light with an illuminance of 20 mW / cm ² (wavelength 365 nm) for 50 seconds in an air atmosphere, and further heated (post-cure) for 1 hour in an oven at 100 ° C. Obtained.
The water contact angle was evaluated about the obtained cured film. The water contact angle was measured by measuring the contact angle after 5 seconds by the θ / 2 method 5 times in a room maintained at 23 ° C. with 1 μL of ion exchanged water on the surface of each cured film, and calculating the average value. The contact angle value was used. The results are also shown in Table 5.

As shown in Table 5, the cured product obtained using the epoxy compound of the present invention exhibits a high water contact angle compared to the cured product obtained using general-purpose epoxy compounds such as HBPA, CEL and TMPTG. (Example 28 and Comparative Examples 11 to 13). Moreover, also when the epoxy compound of this invention was added to the general purpose epoxy compound, the cured | curing material showed the high water contact angle compared with the non-added thing (Examples 29-31 and Comparative Examples 11-13). ).
Furthermore, the hardened | cured material obtained using the epoxy compound of this invention showed the high water contact angle compared with the hardened | cured material obtained using DOX which is a general purpose oxetane compound (Example 28 and Comparative Example 14). ). Moreover, also when the epoxy compound of this invention was added to the general purpose oxetane compound, the cured | curing material showed the high water contact angle compared with the unadded thing (Example 32 and Comparative Example 14).

Claims (16)

An epoxy compound represented by the formula [1].

(Wherein R ¹ represents an alkyl group having 2 to 30 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L represents a carbonyl group or Represents a methylene group, A represents an aliphatic hydrocarbon group which may contain an (n + 1) -valent ether bond, and n represents an integer of 2 to 8. The epoxy compound according to claim 1, wherein R ¹ represents an alkyl group having 6 to 26 carbon atoms. The epoxy compound according to claim 2, wherein R ¹ represents an alkyl group having 14 to 20 carbon atoms. The epoxy compound according to claim 1, wherein R ¹ is a branched alkyl group. A is glycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, ditrimethylolpropane, pentaerythritol, and di The epoxy compound according to any one of claims 1 to 4, which is a group derived by removing a hydroxy group from a polyol selected from the group consisting of pentaerythritol. The epoxy compound according to claim 5, wherein A is a group derived by removing a hydroxy group from a polyol selected from the group consisting of 1,1,1-trimethylolpropane and pentaerythritol. A curable composition comprising (a) the epoxy compound according to any one of claims 1 to 6 and (b) a curing agent. The curable composition according to claim 7, wherein the (b) curing agent is at least one selected from the group consisting of acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, and polymercaptans. The curable composition according to claim 7 or 8, comprising 0.5 to 1.5 equivalents of the (b) curing agent with respect to 1 equivalent of the epoxy group of the (a) epoxy compound. (A) Curability comprising (c) a curing catalyst comprising the epoxy compound according to any one of claims 1 to 6 and (c1) an acid generator and / or (c2) a base generator. Composition. The curable composition according to claim 10, wherein the (c) curing catalyst is (c1) an acid generator. The curable composition according to claim 11, wherein the (c1) acid generator is at least one selected from the group consisting of a photoacid generator and a thermal acid generator. The curable composition according to claim 12, wherein the (c1) acid generator is an onium salt. The curable composition according to claim 13, wherein the acid generator (c1) is a sulfonium salt or an iodonium salt. The curable composition according to any one of claims 11 to 14, comprising 0.1 to 20 parts by mass of the (c1) acid generator with respect to 100 parts by mass of the (a) epoxy compound. . A method for producing an epoxy compound represented by the formula [1], wherein the ene compound represented by the formula [2] is oxidized.

(Wherein R ¹ represents an alkyl group having 2 to 30 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and L represents a carbonyl group or Represents a methylene group, A represents an aliphatic hydrocarbon group which may contain an (n + 1) -valent ether bond, and n represents an integer of 2 to 8.

(In the formula, R ¹ , R ^{2 to} R ⁴ , L, A, and n have the same meaning as described above.)