KR102629442B1 - Epoxy-based reactive diluent and epoxy resin composition containing the same - Google Patents

Abstract

(식 중, R¹ 및 R²는 탄소원자수 2 내지 27의 알킬기, R³은 수소원자 또는 탄소원자수 1 내지 25의 알킬기를 나타내고, 단 -CR¹R²R³기의 탄소원자수의 합계는 10 내지 30이며, X는, *-C(=O)O-, *-CH₂O- 또는 *-CH₂OC(=O)-를 나타내고, L은 단결합, 또는 에테르결합을 포함할 수도 있는 탄소원자수 1 내지 8의 알킬렌기를 나타내고, E는 식[2] 또는 식[3]으로 표시되는 기를 나타낸다.)

(식 중, R⁴ 내지 R¹⁵는 수소원자 또는 탄소원자수 1 내지 10의 알킬기를 나타낸다.)[Problem] To provide an epoxy resin composition containing a low volatility reactive diluent for epoxy resin that does not reduce the physical properties such as heat resistance and curability of the cured product as much as possible and can further provide the effect of lowering the dielectric constant.
[Solution] An epoxy resin composition containing at least one epoxy compound represented by formula [1] and an epoxy resin, and a curable composition containing this resin composition and a curing agent or acid generator.

(In the formula, R ¹ and R ² are an alkyl group having 2 to 27 carbon atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that the total number of carbon atoms of the -CR ¹ R ² R ³ group is 10. to 30, X represents *-C(=O)O-, *-CH ₂ O- or *-CH ₂ OC(=O)-, and L may include a single bond or an ether bond Represents an alkylene group having 1 to 8 carbon atoms, and E represents a group represented by formula [2] or formula [3].)

(In the formula, R ⁴ to R ¹⁵ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

Description

Epoxy-based reactive diluent and epoxy resin composition containing the same

The present invention relates to an epoxy-based reactive diluent and an epoxy resin composition containing the same.

Conventionally, epoxy resins are epoxy resin compositions combined with a curing agent or acid generator, and are used in various fields as paints, adhesives, encapsulants, molding materials, molding materials, etc., for civil engineering and construction, for electrical and electronic parts, and as materials for transportation. It is widely used. And various types of epoxy resins are used depending on the application field or application location.

In liquid molding such as casting molding, liquid epoxy resins such as bisphenol A type epoxy resin are used. However, most of these liquid epoxy resins have high viscosity, and it is difficult to say that they have good workability, so reactive diluents for epoxy resins are widely used for the purpose of adjusting viscosity.

Representative examples of such reactive diluents include alkyl glycidyl ethers such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether, and are intended for use in electronic components, etc. A manufacturing method has also been proposed (for example, patent document 1).

Meanwhile, in the technical field of electrical and electronic component materials, the speed and frequency of signals in various electronic devices are increasing in recent years, and along with this, there is a demand for materials that realize low dielectric constants.

As an example of a low dielectric constant material, a (meth)acrylic polymer containing an alkyl (meth)acrylate having a multi-branched higher alkyl group has been proposed (Patent Document 2). However, acrylic resin is generally considered to be inferior to epoxy resin in heat resistance and adhesion.

Japanese Patent Publication No. 2002-293755 published Japanese Patent Publication No. 2012-246477 published

The reactive diluents made of the alkyl glycidyl ethers described above have a low boiling point and are therefore highly volatile. Depending on the heating conditions during curing of the epoxy resin or melt molding of the resin, there is a problem that the diluent itself volatilizes. When added to the epoxy resin, there were problems such as a significant decrease in heat resistance and curability of the cured product.

Meanwhile, as the performance of various electronic devices increases, their constituent materials are required to have lower dielectric constants in addition to conventional requirements such as heat resistance. In general, the heat resistance and strength of epoxy resins improve as the number of epoxy groups per molecule increases, but on the other hand, an increase in the number of highly polar epoxy groups tends to result in an increase in dielectric constant.

The present invention provides an epoxy resin composition containing a low-volatility reactive diluent for epoxy resin, which can provide the effect of lowering the dielectric constant without reducing the physical properties such as heat resistance and curability of the cured product as much as possible. The purpose is to

In order to achieve the above object, the present inventors have carefully studied and found that the monofunctional epoxy ester or ether compound having a branched alkyl moiety is a liquid compound with a very low viscosity among the liquid epoxy compounds so far, and is also a liquid compound with a very low viscosity compared to conventional epoxy compounds. It was discovered that it had excellent compatibility with resin, and from the results, it was discovered that it was useful as a reactive diluent for epoxy compounds and that it had lower volatility than conventional commercially available reactive diluents (alkyl glycidyl ethers). In addition, the epoxy resin composition obtained by mixing the monofunctional epoxy compound having the branched alkyl moiety and the epoxy resin is mixed with a curing agent or a curing catalyst to form a curable composition, and in the cured product obtained by curing this, the original epoxy resin It was discovered that the dielectric constant could be reduced compared to the cured product and the water absorption could also be maintained at a low state, and the present invention was completed.

That is, the present invention, as a first aspect, relates to an epoxy resin composition containing at least one type of epoxy compound represented by formula [1] and an epoxy resin.

[Formula 1]

(In the formula, R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that -CR ¹ R ² R ³ group The total number of carbon atoms is 10 to 30, and X represents *-C(=O)O-, *-CH ₂ O-, or *-CH ₂ OC(=O)- (where * is -CR ¹ R ² represents a stage bonded to the R ³ group.), L represents a single bond or an alkylene group with 1 to 8 carbon atoms that may include an ether bond, and E is represented by formula [2] or formula [3] It represents energy.)

[Formula 2]

(In the formula, R ⁴ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

As a second aspect, it relates to the epoxy resin composition described in the first aspect, wherein the -CR ¹ R ² R ³ group is a group having 14 to 26 carbon atoms.

As a third aspect, it relates to the epoxy resin composition described in the second aspect, wherein the -CR ¹ R ² R ³ group is a group having 14 to 20 carbon atoms.

As a fourth aspect, it relates to the epoxy resin composition according to any one of the first to third aspects, wherein X is *-C(=O)O-.

As a fifth aspect, it relates to the epoxy resin composition according to any one of the first to third aspects, wherein X is *-CH ₂ O-.

As a sixth aspect, it relates to the epoxy resin composition according to any one of the first to fifth aspects, wherein E is a group represented by formula [2].

As a seventh aspect, it relates to the epoxy resin composition according to any one of the first to sixth aspects, wherein L is a single bond or a methylene group.

As an eighth viewpoint, it relates to a curable composition containing (a) the epoxy resin composition according to any one of the first to seventh viewpoints, and (b) a curing agent.

As a ninth aspect, the curing agent (b) is at least one selected from the group consisting of acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, and polymercaptans. It's about.

As a tenth aspect, it relates to the curable composition according to the eighth or ninth aspect, which contains 0.5 to 1.5 equivalents of the curing agent (b) relative to 1 equivalent of the epoxy group of the epoxy resin composition (a).

As an eleventh aspect, comprising (a) an epoxy resin composition according to any one of the first to seventh aspects, and (c) a curing catalyst consisting of (c1) an acid generator and/or (c2) a base generator, It relates to a curable composition.

As a twelfth aspect, it relates to the curable composition according to the eleventh aspect, wherein the curing catalyst (c) is an acid generator (c1).

As a thirteenth aspect, it relates to the curable composition according to the twelfth 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 fourteenth aspect, it relates to the curable composition according to the thirteenth aspect, wherein the acid generator (c1) is an onium salt.

As a 15th aspect, it relates to the curable composition according to the 14th aspect, wherein the acid generator (c1) is a sulfonium salt or an iodonium salt.

As a 16th aspect, it relates to the curable composition according to any one of the 12th to 15th aspects, comprising 0.1 to 20 parts by mass of the acid generator (c1) relative to 100 parts by mass of the epoxy resin composition (a). .

As a seventeenth aspect, it relates to the use of at least one type of epoxy compound represented by formula [1] as a reactive diluent in an epoxy resin composition.

[Formula 3]

(In the formula, R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that -CR ¹ R ² R ³ group The total number of carbon atoms is 10 to 30, and X represents *-C(=O)O-, *-CH ₂ O-, or *-CH ₂ OC(=O)- (where * is -CR ¹ R ² represents a stage bonded to the R ³ group.), L represents a single bond or an alkylene group with 1 to 8 carbon atoms that may include an ether bond, and E is represented by formula [2] or formula [3] It represents energy.)

[Formula 4]

(In the formula, R ⁴ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

As an eighteenth aspect, it relates to an epoxy compound represented by formula [1a].

[Formula 5]

(In the formula, R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that -CR ¹ R ² R ³ group The number of carbon atoms is 10 to 30, R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and L represents an alkylene group with 1 to 8 carbon atoms that may include an ether bond. .)

The epoxy resin composition of the present invention can be made into a composition with excellent compatibility and handleability by mixing an epoxy resin and a monofunctional epoxy compound having a branched alkyl moiety as a reactive diluent, and can also be used as a reactive diluent based on conventional epoxy resins. Compared to the composition used, a cured product with high heat resistance can be produced. In addition, the epoxy resin composition of the present invention forms a curable composition by mixing a curing agent or a curing catalyst, and the cured product obtained by curing this composition does not contain the monofunctional epoxy compound (reactive diluent) having the branched alkyl moiety. Compared to a cured product produced from the composition, a cured product having a low dielectric constant and low water absorption can be produced.

In addition, the monofunctional epoxy compound having the branched alkyl moiety is an epoxy compound with a very low viscosity (approximately 100 mPa·s or less) among liquid epoxy compounds, and is also a low volatility compound compared to conventional commercially available epoxy-based reactive diluents. Compatibility with liquid epoxy resin is also excellent. Furthermore, an epoxy curable composition produced by mixing this epoxy compound can produce a cured product with a low dielectric constant. Therefore, the monofunctional epoxy compound having the branched alkyl moiety can be suitably used as a reactive diluent for an epoxy resin composition, and thereby not only improves the handling properties and curability of the epoxy resin composition, but also improves the composition. In the cured product produced using it, heat resistance and further low dielectric properties can be imparted.

The epoxy-based reactive diluent of the present invention and the epoxy resin composition containing the same include semiconductor encapsulation materials, transparent encapsulants, adhesives for electronic materials, optical adhesives, printed wiring board materials, interlayer insulating film materials, fiber-reinforced plastics, inks for stereolithography, Various materials such as paint ink, water-repellent coating material, water-repellent coating material, lipophilic coating material, self-healing material, biocompatible material, birefringence control material, pigment dispersant, filler dispersant, rubber modifier, etc., base material, crosslinking agent, It can be suitably used as a diluent, leveling agent, and compatibilizer.

[(a) Epoxy resin composition]

The present invention relates to an epoxy resin composition containing at least one type of epoxy compound represented by the following formula [1] and an epoxy resin, and further relates to an epoxy resin composition of the epoxy compound represented by the following formula [1]: Use as a reactive diluent is also a subject of the present invention.

<Epoxy compound>

The epoxy compound contained in the epoxy resin composition of the present invention is represented by the following formula [1].

[Formula 6]

In the above formula, R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that -CR ¹ R ² R ³ group The total number of carbon atoms is 10 to 30, and X represents *-C(=O)O-, *-CH ₂ O-, or *-CH ₂ OC(=O)- (where * is -CR ¹ R ² represents a stage bonded to the R ³ group.), L represents a single bond or an alkylene group with 1 to 8 carbon atoms that may include an ether bond, and E is represented by formula [2] or formula [3] It represents energy.

[Formula 7]

In the above formula, R ⁴ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

The alkyl group having 2 to 27 carbon atoms for R ¹ and R ² may have not only a straight chain structure but also a branched structure or a cyclic structure.

Specifically, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetra. Decyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (aralkyl group) ), linear alkyl groups such as henicosyl group, docosyl group (behenyl group), tricosyl group, tetracosyl group (lignoseryl group), pentacosyl group, hexacosyl group, and heptacosyl group; 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-methyl Hexyl group, 5-methylhexyl group, 2-ethylpentyl group, heptan-3-yl group, heptan-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethyl Pentan-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-methylheptane -2-yl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3 -Ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, 9-methyldecyl group, undecane-5 -yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-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-methyltride Syl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecan-8-yl group, heptadecan-9-yl group , 3,13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecan-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group, nonadecane -9-yl group, nonadecan-10-yl group, 2,6,10,14-tetramethylpentadecan-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosan-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosan-12-yl 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 Branched chain alkyl groups such as -13-yl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo [2.2. 1]heptan-2-yl group, bornyl (ボルニル) 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 ] alicyclic alkyl groups such as decan-8-yl group and cyclododecyl group.

R ¹ and R ² are each independently, preferably an alkyl group having 4 to 16 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.

Among them, R ¹ and R ² are each independently preferably a branched alkyl group, more preferably a branched alkyl group with 4 to 16 carbon atoms, and even more preferably a branched alkyl group with 6 to 10 carbon atoms. .

Specifically, R ¹ and R ² are each independently hexyl group, heptyl group, octyl group, nonyl group, 4,4-dimethylpentan-2-yl group, 6-methylheptan-2-yl group, 6-methylocyl group. Tyl group, 3,5,5-trimethylhexyl group, and 3,7-dimethyloctyl group are particularly preferable.

The alkyl group having 1 to 25 carbon atoms for R ³ may have not only a straight chain structure, but also a branched structure or a cyclic structure.

Such alkyl groups having 1 to 25 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (ra) Uryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group , straight-chain alkyl groups such as icosyl group (aralkyl group), henicosyl group, docosyl group (behenyl group), tricosyl group, tetracosyl group (lignoseryl group), and pentacosyl group; 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, heptan-3-yl group, heptan-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-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- Diyl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptane -3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, 9-methyldecyl group, undecane-5-yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, 10-methylundecyl group, 11-methyldodecyl group, tridecane -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, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecan-8-yl group, heptadecan-9-yl group, 3, 13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecan-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group, nonadecan-9- diyl group, nonadecan-10-yl group, 2,6,10,14-tetramethylpentadecan-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, henicosan-10-yl group, 20-methyl Henicosyl group, 21-methyldocosyl group, tricosan-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosan-12-yl group, branched alkyl groups such as pentacosan-13-yl group, 2,22-dimethyltricosan-11-yl group, 3,21-dimethyltricosan-11-yl group, and 9,15-dimethyltricosan-11-yl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, 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} ]alicyclic alkyl groups such as decan-8-yl group and cyclododecyl group.

Among these, R ³ is preferably a hydrogen atom.

The group having R ¹ , R ² and R ³ : -CR ¹ R ² R ³ group has a total number of carbon atoms of 10 to 30, preferably a group of 14 to 26 carbon atoms, and particularly preferably a carbon source. It is a flag of 14 to 20 embroidery.

Specific examples of the -CR ¹ R ² R ³ group include 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, undecane-5-yl group, 3-ethylnonan-3-yl group, 5 -Ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, tridecan-6-yl group, tridecan-7-yl group, 7-ethylundecan-2-yl group, 3-ethylundecan-3-yl group, 5-ethylundecan-5-yl group, pentadecane-7-yl group, pentadecane-8-yl group, heptadecan-8-yl group, heptadecan-9-yl group, 3, 13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecan-5-yl group, nonadecan-9-yl group, nonadecan-10-yl group, 2,6,10 , 14-tetramethylpentadecan-7-yl group, henicosan-10-yl group, tricosan-11-yl group, pentacosan-12-yl group, pentacosan-13-yl group, 2,22-dimethyltricosan-11 -yl group, 3,21-dimethyltricosan-11-yl group, 9,15-dimethyltricosan-11-yl group, heptacosane-13-yl group, nonacosan-14-yl group, etc.

_Said

Examples of the alkylene group having 1 to 8 carbon atoms that may contain an ether bond in L include methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, and pentamethylene group. group, 2,2-dimethyltrimethylene group, hexamethylene group, heptamethylene group, octamethylene group, 2-oxatetramethylene group, 2,5-dioxaheptamethylene group, 2,5,8-trioxadecamethylene group, 2-oxa-3-methyltetramethylene group, 2,5-dioxa-3,6-dimethylheptamethylene group, etc.

The L is preferably a methylene group, trimethylene group, hexamethylene group, or 2-oxatetramethylene group, and more preferably a methylene group.

The group represented by formula [2] or formula [3], which is E in the above formula [1], is an epoxy-containing group.

The alkyl group having 1 to 10 carbon atoms for R ⁴ to R ¹⁵ in formula [2] or formula [3] includes methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 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, decyl group, etc.

Among them, it is preferable that R ⁴ to R ¹⁵ are hydrogen atoms.

Meanwhile, among the epoxy compounds represented by the above formula [1], the compound represented by the following formula [1a] is also subject to the invention.

[Formula 8]

In the formula, R ¹ and R ² each independently represent an alkyl group having 2 to 27 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that the carbon source of the group -CR ¹ R ² R ³ The number is 10 to 30, R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and L represents an alkylene group with 1 to 8 carbon atoms that may include an ether bond.

The specific groups of R ¹ to R ⁶ and L are as described above.

The compound represented by the formula [1] is a conventionally known epoxy (for example, described in the pamphlet of International Publication No. 2012/128325, Japanese Patent Publication No. 2012-25688, etc.) using carboxylic acids or alcohols as starting materials. It can be manufactured by the synthetic method of De.

For example, ^{in the case} where An ester compound (intermediate) with an unsaturated bond is formed by reacting (anhydride, acid azide, active ester, etc.) with an allyl halide or an alcohol having an allyl group, and then reacting this intermediate with peroxide to epoxidize the unsaturated bond. It can be manufactured by In addition, it can also be produced by reacting carboxylic acid represented by R ¹ R ² R ³ C-COOH with epichlorohydrin and ring closing. As an example, a synthesis scheme in the case where E is a group represented by formula [2] is shown below.

[Formula 9]

In ^addition , ⁱⁿ the case ^of _{an ether} compound in which It can be produced by reacting to form an ether compound (intermediate) having an unsaturated bond, and then reacting this intermediate with peroxide to epoxidize the unsaturated bond.

The carboxylic acid represented by R ¹ R ² R ³ C-COOH and the alcohol represented by R ¹ R ² R ³ C-CH ₂ OH can be commercially available, for example, the R ¹ R ² R ³ C Compounds represented by -COOH include Fineoxochol (registered trademark) isopalmitic acid, isostearic acid, isostearic acid N, isostearic acid T, and isoaracnic acid manufactured by Nissan Chemical Industries, Ltd. can be mentioned. In addition, the compounds represented by R ¹ R ² R ³ C-CH ₂ OH include Fineoxocol (registered trademark) 1600, No. 180, No. 180N, No. 180T, and No. 2000 manufactured by Nissan Chemical Industries, Ltd. I can hear it.

<Epoxy Resin>

The epoxy resin contained in the epoxy resin composition of the present invention generally refers to an epoxy compound having at least two epoxy groups in the molecule, and in the present invention, there is no particular limitation, and various epoxy resins, including commercial products, can be used.

From the viewpoint of handling, it is preferable to use a liquid epoxy resin for the epoxy resin composition of the present invention. On the other hand, if the epoxy resin is solid or has a very high viscosity, it can be dissolved in a solvent for convenience in handling, or, as described later, it can be heated to a level where the curing reaction does not proceed when preparing the epoxy resin composition. there is. However, the addition of a solvent may cause a decrease in the density of the cured product due to evaporation of the solvent, or a decrease in strength and water resistance due to the creation of pores. For this reason, it is preferable to employ the epoxy resin itself in a liquid state at room temperature and under normal pressure.

Epoxy resins usable in the present invention include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, (poly)ethylene glycol diglycidyl ether, and (poly)propylene glycol dily. Glycidyl 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, tetraglycidyl metaxylenediamine, 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. Dyl ether, resorcinol diglycidyl ether, diglycidyl phthalate, diglycidyl tetrahydrophthalate, neopentyl glycol diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, triglycidyl isocidyl ether. Anurate, Tris-(3,4-epoxybutyl)isocyanurate, Tris-(4,5-epoxypentyl)isocyanurate, Tris-(5,6-epoxyhexyl)isocyanurate, Tris- (7,8-epoxyoctyl)isocyanurate, tris(2-glycidyloxyethyl)isocyanurate, monoallyldiglycidylisocyanurate, N,N'-diglycidylN' '-(2,3-dipropionyloxypropyl)isocyanurate, N,N'-bis(2,3-dipropionyloxypropyl)N''-glycidylisocyanurate, tris(2 ,2-bis(glycidyloxymethyl)butyl)3,3',3''-(2,4,6-trioxo-1,3,5-triazine-1,3,5-triyl) Tripropanoate, sorbitol polyglycidyl ether, diglycidyl adipic acid, diglycidyl o-phthalate, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1, 6-dimethylolperfluorohexanediglycidyl 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'-methylcyclohexyl Examples include methyl, ethylene glycol bis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl)adipate, and bis(2,3-epoxycyclopentyl)ether. It is not limited.

These epoxy resins can be used individually or as a mixture of two or more types.

Meanwhile, examples of the epoxy resin include the following commercial products.

Examples of solid epoxy resins include TEPIC (registered trademark)-G, S, L, and HP (all manufactured by Nissan Chemical Industries, Ltd.).

In addition, liquid epoxy resins include TEPIC (registered trademark) - PAS B22, PAS B26, PAS B26L, VL, UC, FL (all manufactured by Nissan Chemical Industries, Ltd.), and jER (registered trademark) 828. , YX8000 [all manufactured by Mitsubishi Chemical Corporation], Rikka Resin (registered trademark) DME100 [manufactured by Nippon Ewha Corporation], and Celoxide 2021P [manufactured by Daicel Corporation].

In the epoxy resin composition of the present invention, the mixing ratio of the epoxy compound represented by formula [1] and the epoxy resin is mass ratio, epoxy compound represented by formula [1]: epoxy resin = 3:97 to 60:40. It is preferable to set it in the range, and it is more preferable to set it in the range of 5:95 to 40:60. By setting the blending amount of the epoxy compound represented by formula [1] to the above ratio or more, a sufficient viscosity lowering effect is obtained, which also leads to a sufficient reduction in dielectric constant in the resulting resin composition. Additionally, by keeping the blending amount of the epoxy compound represented by formula [1] below the above ratio, a decrease in crosslink density can be suppressed and the heat resistance and mechanical properties of the cured product obtained later can be maintained.

The epoxy resin composition of the present invention can be produced by mixing the epoxy compound represented by the formula [1] and the epoxy resin, and this mixing is not particularly limited as long as it can be mixed uniformly, for example, using a mixer or It can be carried out using a kneader and, taking viscosity into consideration, under heating as needed. For example, it can be prepared by mixing at a temperature of 10 to 150°C for about 0.5 to 10 hours.

[(b) Curing agent and curable composition containing the same]

The present invention is directed to a curable composition containing the above-described epoxy resin composition and (b) a curing agent. In this curable composition, a curing accelerator can be used in combination with the curing agent (b).

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. These curing agents can be used as solids by dissolving them in a solvent. However, evaporation of the solvent causes a decrease in the density of the cured product and a decrease in strength and water resistance due to the creation of pores, so it is preferable that the curing agent itself is liquid at room temperature and pressure.

The curing agent is present in an amount of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, based on 1 equivalent of the epoxy group in the epoxy resin composition (a), that is, the entire epoxy compound and epoxy resin represented by the formula [1] described above. It can be contained in a ratio of . The equivalent weight of the curing agent to the epoxy compound is expressed as the equivalent ratio of the curable group of the curing agent to the epoxy group.

The acid anhydride is preferably an anhydride of a compound having multiple carboxyl groups in one molecule. These acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, and tetrahydromellitic anhydride. Phthalic acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, anhydrite Acidic acid, methylcyclohexenedicarboxylic acid anhydride, chlorendic acid anhydride, etc. can be mentioned.

Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylhymic anhydride), hydrogenated methylnadic anhydride, and methylbutenyl are liquid at room temperature and pressure. Tetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and mixtures of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride are preferred. These liquid acid anhydrides have a viscosity of about 10 to 1,000 mPa·s when measured at 25°C. For acid anhydride groups, one acid anhydride group is calculated as one equivalent.

Amines include, for example, piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, and 2-(dimethylaminomethyl)phenol. , diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthanediamine, isophoronediamine, Diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc. are mentioned. Among these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, bis(1-methyl-2-aminocyclohexyl)methane, menthanediamine, Isophorone diamine, diaminodicyclohexylmethane, etc. can be preferably used.

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

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

Imidazoles include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxyimidazole adduct. etc. can be mentioned.

Polymercaptans, for example, have a mercaptan group at the end of a polypropylene glycol chain or a mercaptan group at the end of a polyethylene glycol chain, and are preferably in a liquid form.

Additionally, when obtaining a cured product from the curable composition of the present invention, a curing accelerator (also referred to as a curing aid) may be used together as appropriate.

Examples of the curing accelerator 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]undeca-7-ene, salt of 1,8-diazabicyclo[5.4.0]undeca-7-ene and octylic acid, zinc octylate, tetrabutylammonium and quaternary ammonium salts such as bromide. In addition, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and amines such as 2,4,6-tris(dimethylaminomethyl)phenol and benzyldimethylamine as the curing agents mentioned above. It can also be used as a curing accelerator for other types of curing agents.

These curing accelerators can be used in a ratio of 0.001 to 0.1 parts by mass per 1 part by mass of the curing agent.

In the present invention, a curable composition is obtained by mixing the curing agent (b) and, if necessary, a curing accelerator into an epoxy resin composition containing an epoxy compound and an epoxy resin represented by the formula [1].

Mixing of these components is not particularly limited as long as they can be mixed uniformly, but it is preferable to use, for example, a reaction flask and a stirring blade or a mixer, or to use a kneader, for example, using a rotating stirrer. It is preferable to carry out under sufficient stirring.

Mixing is performed under heating as necessary considering viscosity, and is performed at a temperature of 10 to 100°C for 0.5 to 1 hour. When the viscosity of the epoxy resin composition is high and uniform mixing does not proceed quickly, the viscosity is reduced and operability is improved by heating to a level where the curing reaction does not proceed.

In addition, as described above, when an epoxy compound dissolved in a solvent is used as an epoxy compound or a solvent is included in the curing agent, the solvent may also be included in the resulting curable composition. Since it may be a factor in causing performance degradation, it is preferable to remove the solvent from the curable composition before forming the cured product by performing pressure reduction or heat treatment during or after preparation of the curable composition.

The obtained curable composition has an appropriate viscosity for use as, for example, a liquid encapsulant. The curable composition of the present invention can be adjusted to an arbitrary viscosity, and can be partially encapsulated in an arbitrary location for use as a transparent encapsulating material for LEDs, etc. by casting, potting, dispenser, printing, etc. . A cured epoxy resin product is obtained by directly mounting the curable composition in its liquid form on an LED or the like using the method described above, followed by drying and curing.

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 injecting it into a mold plate coated with a mold release agent, and then cured at a temperature of 120 to 200 ° C. It is obtained by post-curing).

The heating time is 1 to 12 hours, for example, about 2 to 5 hours for both pre-curing and main curing.

The thickness of the coating film obtained from the curable composition of the present invention can be selected in the range of about 0.01 μm to 10 mm depending on the intended use of the cured product.

[(c) Curing catalyst and curable composition containing the same]

The present invention also applies to the curable composition containing the above-described epoxy resin composition and (c) a curing catalyst. (c) The curing catalyst consists of (c1) an acid generator and/or (c2) a base generator.

<(c1) acid generator>

(c1) As the acid generator, a photoacid generator or a thermal acid generator can be used, and these are not particularly limited as long as they produce an acid (Lewis acid or Bransted acid) directly or indirectly by light irradiation or heating. .

Specific examples of photoacid generators include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complex compounds, iron arene complex compounds, disulfone-based compounds, sulfonic acid derivative compounds, triazine-based compounds, Acetophenone derivative compounds, diazomethane-based compounds, etc. can be mentioned.

Among the above onium salts, iodonium salts include, for example, diphenyl iodonium, 4,4'-dichlorodiphenyl iodonium, 4,4'-dimethoxydiphenyl iodonium, and 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, chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetra Diaryliodonium salts such as kiss (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroacetate, and hexafluoroantimonate can be mentioned.

Examples of the sulfonium salt include triphenylsulfonium, diphenyl(4-tert-butylphenyl)sulfonium, tris(4-tert-butylphenyl)sulfonium, and diphenyl(4-methoxyphenyl)sulfonium. Phonium, tris(4-methylphenyl)sulfonium, tris(4-methoxyphenyl)sulfonium, tris(4-ethoxyphenyl)sulfonium, diphenyl(4-(phenylthio)phenyl)sulfonium, tris(4) -Sulfonium such as (phenylthio)phenyl)sulfonium, chloride, bromide, trifluoromethane sulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroacetate, hexafluoroantimonate, etc. Triaryl sulfonium salts may be mentioned.

Examples of the phosphonium salt include tetraphenylphosphonium, ethyltriphenylphosphonium, tetra(p-methoxyphenyl)phosphonium, ethyltri(p-methoxyphenyl)phosphonium, and benzyltriphenylphosphonium. and arylphosphonium salts of phosphonium such as chloride, bromide, tetrafluoroborate, 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 individually or in combination of two or more types.

Examples of the thermal acid generator include sulfonium salts and phosphonium salts, and examples of these compounds include compounds cited as examples of various onium salts in the above-mentioned photoacid generators. Additionally, benzyl(4-hydroxyphenyl)(methyl)sulfonium hexafluoroantimonate and the like can be suitably used.

These thermal acid generators can be used individually or in combination of two or more types.

Among these, as the (c1) acid generator, a sulfonium salt compound or an iodonium salt compound is preferable, and for example, a compound having an anionic species such as hexafluorophosphate or hexafluoroantimonate, which exhibits strong acidity, is preferable.

(c1) The acid generator can be contained in a ratio of 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the (a) epoxy resin composition. .

<(c2) base generator>

(c2) As the base generator, a photobase generator or a thermobase generator can be used, and these are specifically limited as long as they generate a base (Lewis base or Bransted base) directly or indirectly by light irradiation or heating. It doesn't work.

Examples of the photobase generator include alkylamine-based photobase generators such as 9-anthrylmethyl=N,N-diethylcarbamate; 9-Anthryl=N,N-dicyclohexylcarbamate, 1-(9,10-anthraquinon-2-yl)ethyl=N,N-dicyclohexylcarbamate, dicyclohexylammonium=2-(3 -benzoylphenyl)propionate, 9-anthryl=N-cyclohexylcarbamate, 1-(9,10-anthraquinon-2-yl)ethyl=N-cyclohexylcarbamate, cyclohexylammonium=2-( Cycloalkylamine-based photobase generators such as 3-benzoylphenyl)propionate and (E)-N-cyclohexyl-3-(2-hydroxyphenyl)acrylamide; 9-anthrylmethyl=piperidine-1-carboxylate, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one, (2-nitrophenyl) Piperidine-based photobase generators such as methyl=4-hydroxypiperidine-1-carboxylate and (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-tetramethylbiguanidium=n-butyltriphenylborate, 1,5,7-triazabicyclo[4.4.0]deca-5-enium=2 -Guanidine-based photobase generators such as (9-oxoxanthen-2-yl)propionate; and imidazole-based photobase generators such as 1-(9,10-anthraquinon-2-yl)ethyl=imidazole-1-carboxylate.

These photobase generators can be used individually or in combination of two or more types.

In addition, photobase generators are available as commercial products, for example, photobase generator WPBG series (WPBG-018, No. 027, No. 082, No. 140, No. 266, No. 300) manufactured by Wako Pure Chemical Industries, Ltd. etc.) can be used conveniently.

Examples of the thermobase generator include carbamates such as 1-methyl-1-(4-biphenylyl)ethyl carbamate and 2-cyano-1,1-dimethylethyl carbamate; Urea, such as urea and N,N-dimethyl-N'-methylurea; Guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate, and guanidine phenylpropiolate; Dihydropyridines such as 1,4-dihydronicotinamide; N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2, Dimethylpiperidines such as 6-dimethylpiperidine; Quaternary ammonium salts such as tetramethylammonium phenylsulfonylacetate and tetramethylammonium phenylpropiolate; Dicyandiamide, etc. can be mentioned. In addition, the salt of 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), U-CAT (registered trademark) SA810, SA831, SA841, SA851 [above, San-Apro Co., Ltd. ) 1st], etc. may be mentioned.

These thermobase generators can be used individually or in combination of two or more types.

(c2) The base generator can be contained in a ratio of 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the epoxy resin composition (a). .

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

In the present invention, the curable composition containing the above-described epoxy resin composition and (c) a curing catalyst can be applied onto a substrate and cured by light irradiation or heating. Additionally, additional heating may be performed before or after light irradiation.

Methods for applying the curable composition of the present invention on a substrate include, for example, flow coating, spin coating, spray coating, screen printing, flexographic printing, inkjet printing, casting, and bar coating. , curtain coating method, roll coating method, gravure coating method, dipping method, slit method, etc.

The thickness of the coating film formed from the curable composition of the present invention can be selected in the range of about 0.01 μm to 10 mm depending on the use of the cured product, for example, when used for photoresist, 0.05 to 10 μm (especially 0.1 to 5 μm). When used for printed wiring boards, it can be set to around 10 μm to 5 mm (especially 100 μm to 1 mm), and when used for optical thin films, it can be set to around 0.1 to 100 μm (especially 0.3 to 50 μm).

(c) In the curable composition containing a curing catalyst, the light for irradiation or exposure when using a photoacid generator or photobase generator includes, for example, gamma rays, X-rays, ultraviolet rays, visible light, etc. Usually, visible light or ultraviolet rays, especially ultraviolet rays, are often used.

The wavelength of light is, for example, 150 to 800 nm, preferably 150 to 600 nm, more preferably 200 to 400 nm, and especially 300 to 400 nm.

The exposure amount varies depending on the thickness of the coating film, but can be, for example, 2 to 20,000 mJ/cm ² , preferably about 5 to 5,000 mJ/cm ² .

The light source can be selected depending on the type of light to be exposed. For example, in the case of ultraviolet rays, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, deuterium lamp, 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.

(c) In the curable composition containing a curing catalyst, when using a thermal acid generator or a thermobase generator, or using a photoacid generator or a photobase generator, heating of the coating film performed as necessary after light irradiation is, For example, it is carried out at room temperature (approximately 23°C) to approximately 250°C. The heating time can be selected from a range of 3 seconds or more (for example, from 3 seconds to about 5 hours), for example, from 5 seconds to about 2 hours.

Furthermore, when forming a pattern or image (for example, when manufacturing a printed wiring board, etc.), the coating film formed on the substrate may be pattern exposed. This pattern exposure can be performed by scanning laser light, or by irradiating light through a photomask. A pattern or image can be formed by developing (or dissolving) the non-irradiated area (unexposed area) created by such pattern exposure with a developer.

As a developer, an aqueous alkaline solution or an organic solvent can be used.

Examples of the aqueous alkaline solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; Aqueous solutions of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine.

The alkaline developer is generally an aqueous solution of 10% by mass or less, and an aqueous solution of 0.1 to 3% by mass is preferably used. Additionally, alcohols or surfactants can be added to the developer, and the amount of these additions is preferably 0.05 to 10 parts by mass per 100 parts by mass of the developer. Specifically, a 0.1 to 2.38% by mass aqueous solution of tetramethylammonium hydroxide, etc. can be used.

In addition, the organic solvent used as a developer can be a general organic solvent, for example, aromatic hydrocarbons such as toluene; Ester such as ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl 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; Alcohols such as methanol, ethanol, 2-propanol, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether can be mentioned. These can be used individually or as a mixture of two or more types.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), etc. can be preferably used.

[solvent]

The curable composition containing the above-mentioned epoxy resin composition and (b) a curing agent, and the curable composition containing the epoxy resin composition and (c) a curing catalyst may contain a solvent as needed.

In the (a) epoxy resin composition of the present invention, the epoxy compound represented by formula [1] serves as a reactive diluent, and is mixed with the above-described (b) curing agent or (c) curing catalyst to prepare the present invention. Since a curable composition is obtained, there is basically little need to use a solvent, but it is possible to add a solvent as needed.

For example, as in the case where (b) the curing agent described above is solid, (c) the curing catalyst is solid, a curable composition can be prepared by dissolving the curing catalyst in a solvent such as propylene carbonate and mixing it with a liquid epoxy resin. there is. Additionally, even when an acid generator or the like is dissolved in the (a) epoxy resin composition, a general solvent may be added to adjust the viscosity of the resulting curable composition.

Examples of solvents 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, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, 3- Hydroxy esters such as butyl hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and methyl 2-hydroxy-3-methylbutanoate; Methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, Propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate. , 2-methoxybutyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropyl propionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-Butoxypropionate, butyl 2-butoxypropionate, 3-methoxymethyl propionate, ethyl 3-methoxypropionate, 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxymethyl propionate, 3 -Ethyl ethoxypropionate, 3-ethoxypropyl propionate, 3-ethoxybutyl propionate, 3-methyl propionate, ethyl 3-propoxypropionate, 3-propoxypropionate, 3-butyl propoxypropionate, 3- Methyl butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropyl propionate, butyl 3-butoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether 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 esters such as ether propionate; Ketones such as methyl ethyl ketone (MEK), 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 glycol monopropyl ether, propylene glycol mono Alcohols such as butyl ether; and ethers such as tetrahydrofuran (THF), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

In the curable composition of the present invention, the solid content ratio when the solvent is mixed can be 1 to 100% by mass, or 5 to 100% by mass, or 50 to 100% by mass, or 80 to 100% by mass. Solid content is the ratio of the remaining components after removing the solvent from the curable composition.

[Other curable monomers]

In the curable composition of the present invention, vinyl group-containing compounds, oxetanyl group-containing compounds, etc. may be added as cationic curable monomers other than epoxy resins for the purpose of adjusting viscosity or improving curability.

The vinyl group-containing compound is not particularly limited as long as it is a compound having a vinyl group, and examples include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), and 2-hydroxybutyl vinyl ether ( HBVE), vinyl ether compounds such as triethylene glycol divinyl ether, etc. are mentioned. Additionally, vinyl compounds having a substituent such as an alkyl group or an allyl group at the α-position and/or β-position can also be used. In addition, vinyl ether compounds containing cyclic ether groups such as epoxy groups and/or oxetanyl groups can be used, for example, oxynorbornene divinyl ether, 3,3-dimethanoloxetane divinyl ether, etc. .

Additionally, compounds having a vinyl group and a (meth)acrylic group can be used, for example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, etc.

These vinyl group-containing compounds can be used individually or in combination of two or more types.

The oxetanyl group-containing compound is not particularly limited as long as it is a compound having an oxetanyl group, and includes 3-ethyl-3-(hydroxymethyl)oxetane (OXA) and 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), oxetanylsil Oxetane compounds, such as sesquioxane (OX-SQ) and phenol novolax oxetane (PNOX-1009), etc. are mentioned.

Additionally, compounds having an oxetanyl group and a (meth)acryl group can be used, for example, (3-ethyl-3-oxetanyl)methyl (meth)acrylate.

These oxetanyl group-containing compounds can be used individually or in combination of two or more types.

[Other ingredients]

The curable composition containing the above-described epoxy resin composition and (b) a curing agent, and the curable composition containing the epoxy resin composition and (c) a curing catalyst may contain customary additives as needed. These additives include, for example, pigments, colorants, thickeners, acid generators, antifoaming agents, leveling agents, applicability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, and adhesion promoters. , dissolution accelerators, fillers, antistatic agents, hardeners, etc. These additives may be used individually or in combination of two or more.

For example, a surfactant may be added to the curable composition of the present invention for the purpose of improving applicability. Such surfactants include, but are not limited to, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. The above surfactants can be used individually or in combination of two or more types.

Among these surfactants, fluorine-based surfactants are preferable due to their high applicability improvement effect. Specific examples of fluorine-based surfactants include, for example, Ftop (registered trademark) EF-301, EF-303, EF-352 (all manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megapak (registered trademark) ) F-171, F-173, F-482, R-08, R-30, R-90, BL-20 [all made by DIC Co., Ltd.], Florad FC-430, etc. FC-431 [all manufactured by 3M Japan Co., Ltd.], Asahi Guard (registered trademark) AG-710 [all manufactured by Asahi Glass Co., Ltd.], Surfron S-382, SC-101, SC-102, SC -103, SC-104, SC-105, SC-106 (all manufactured by AGC Semichemical Co., Ltd.), etc., but are not limited to these.

The amount of surfactant added in the curable composition of the present invention is 0.01 to 5% by mass, preferably 0.01 to 3% by mass, more preferably, based on the mass of the solid content (total components excluding solvent) of the curable composition. is 0.01 to 2% by mass.

Additionally, an adhesion promoter may be added to the curable composition of the present invention for the purpose of improving adhesion to the substrate after development. These adhesion accelerators include, for example, chlorotrimethylsilane, trichloro(vinyl)silane, chloro(dimethyl)(vinyl)silane, chloro(methyl)(diphenyl)silane, chloro(chloromethyl)(dimethyl)silane, etc. chlorosilanes; Methoxytrimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, ethoxy(dimethyl)(vinyl)silane, dimethoxydiphenylsilane, triethoxy(phenyl)silane, 3-chloropropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, trimethoxy(3-(N-piperidinyl)propyl)silane alkoxysilanes such as; Silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyl(trimethylsilyl)amine, and trimethylsilylimidazole; Imidazole, indazole, benzoimidazole, benzotriazole, mercaptoimidazole, mercaptopyrimidine 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, ura nitrogen-containing heterocyclic compounds such as sol and thiouracil; Urea or thiourea such as 1,1-dimethylurea and 1,3-dimethylurea can be mentioned. These adhesion promoters can be used individually or in combination of two or more types.

The amount of the adhesion promoter added in the curable composition of the present invention is usually 20% by mass or less, preferably 0.01 to 10% by mass, more preferably 0.01 to 10% by mass, based on the mass of the solid content (total components without solvent) of the curable composition. is 0.05 to 5 mass%.

Furthermore, the curable composition of the present invention may contain a sensitizer. Sensitizers that can be used include anthracene, phenothiazene, perylene, thioxanthone, and benzophenonethioxanthone. In addition, the sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, and cyanine dyes. Pigments, rhodamine-based pigments, and pyrylium salt-based pigments are examples. Particularly preferred are anthracene-based sensitizers, which, when used in combination with a cationic curing catalyst (radiative cationic polymerization initiator), not only dramatically improve sensitivity, but also have a radical polymerization initiator function. For example, cationic curing systems and radicals When adopting a hybrid type that uses a curing system in combination, the catalyst species can be simple. As specific anthracene compounds, dibutoxyanthracene, dipropoxyanthraquinone, etc. are effective.

In addition, when using a base generator as a curing catalyst, sensitizers include, for example, acetophenones, benzoins, benzophenones, anthraquinones, xanthone, thioxanthone, ketal, tertiary amine, etc. I can hear it.

The amount of the sensitizer added 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 mass of the solid content (total components with solvent removed) of the curable composition.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Meanwhile, in the examples, the equipment and conditions used for sample preparation and physical property analysis are as follows.

(1) ^1H NMR spectrum (300MHz)

Device: JNM-ECX300 manufactured by JEOL RESONANCE Co., Ltd.

Standard: tetramethylsilane (0.00ppm)

(2) ^1H NMR spectrum (400MHz)

Device: INOVA-400 manufactured by Varian

Standard: tetramethylsilane (0.00ppm)

(3) GC (gas chromatograph)

Device: GC-2010 Plus manufactured by Shimadzu Corporation

Detector: FID

Column: Agilent J&W GC column HP-5 manufactured by Agilent Technology Co., Ltd. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm)

Injection volume: 1.0μL

Inlet temperature: 250℃

Column temperature: 40°C (5 minutes), temperature increased to 300°C at 20°C/min, 300°C (12 minutes)

(4) GC-MS (gas chromatography mass spectrometry)

Device: GCMS-QP2010 Ultra manufactured by Shimadzu Corporation

Column: Agilent J&W GC column HP-5 manufactured by Agilent Technology Co., Ltd. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm)

Injection volume: 2.0μL

Inlet temperature: 250℃

Column temperature: 40°C (5 minutes), temperature increased to 300°C at 20°C/min, 300°C (12 minutes)

(5) Viscosity

Device: TVE-22L, TVE-25H manufactured by Toki Sangyo Co., Ltd.

(6) melting point

Device: DSC 204 F1 Phoenix manufactured by NETZSCH

(7) Epoxy equivalent

Device: Potentiometric automatic titration device AT-510 manufactured by Kyoto Electronics Co., Ltd.

(8) 5% weight loss temperature (Td5 _% )

Device: Thermo plus EVO/TG-DTA TG8120 manufactured by Rigaku Co., Ltd.

(9) Relative permittivity

Device: E4980A Precision LCR meter manufactured by Keysight Technologies.

Sample holder: Type 12962 room temperature sample holder made by Toyo Technica Co., Ltd.

(10) Glass transition point (Tg)

Device: Thermomechanical measuring device Q400 manufactured by TA Instruments Japan Co., Ltd.

Deformation mode: expansion

Load: 0.05N

Temperature increase rate: 5℃/min

(11) Agitation degassing

Device: Rotating/rotating mixer Awatori Rentaro (registered trademark) ARE-310 made by Shinki Co., Ltd.

(12) Oven

Device: Yamato Science Co., Ltd., blowing low-temperature thermostat DNF400

(13) Hot plate

Device: Yamato Science Co., Ltd., blowing low-temperature thermostat DNF400

(14) UV exposure

Device: US5-0201 manufactured by iGraphics Co., Ltd.

Lamp: H02-L41 manufactured by iGraphics Co., Ltd.

In addition, the abbreviated symbols indicate the following meanings.

IAA: 5,9-dimethyl-2-(1,5-dimethylhexyl)decanoic acid [Fineoxocol (registered trademark) isoaracnic acid manufactured by Nissan Chemical Industries, Ltd.]

IPA: 2-hexyldecanoic acid [Fineoxocol (registered trademark) isopalmitic acid manufactured by Nissan Chemical Industries, Ltd.]

ISA: 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid [Fineoxocol (registered trademark) isostearic acid manufactured by Nissan Chemical Industries, Ltd.]

ISAN: 8-methyl-2-(4-methylhexyl)decanoic acid [Fineoxocol (registered trademark) isostearic acid N manufactured by Nissan Chemical Industries, Ltd.]

ISAT: 2-octyldecanoic acid [Fineoxocol (registered trademark) isostearic acid T manufactured by Nissan Chemical Industries, Ltd.]

ISOL: 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctan-1-ol [Fineoxocol (registered trademark) 180 manufactured by Nissan Chemical Industries, Ltd.]

PA: Palmitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

ωIPA: 14-methylpentadecanoic acid (manufactured by Aldrich)

ωISA: 16-methylheptadecanoic acid (manufactured by Aldrich)

AllBr: Allyl bromide (manufactured by Kanto Chemical Co., Ltd.)

CHMA: 3-cyclohexenylmethanol (manufactured by Aldrich)

ECH: Epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.)

EGMAE: Ethylene glycol monoallyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

OEO: 7-octen-1-ol [Curare Co., Ltd., purity 95%]

PEO: 4-penten-1-ol [manufactured by Tokyo Chemical Industry Co., Ltd.]

DMAP: 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.)

EDC: 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

TMAC: Tetramethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

mCPBA: m-chloroperbenzoic acid [manufactured by Wako Pure Chemical Industries, Ltd., purity 70%]

BGE: Butyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

EHGE: 2-ethylhexyl=glycidyl=ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

SGEs: Glycidyl stearate (manufactured by Tokyo Chemical Industry Co., Ltd.)

BPA: Bisphenol A type epoxy resin [jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation]

CEL: 3,4-epoxycyclohexanecarboxylic acid (3,4-epoxycyclohexyl)methyl [Celoxide 2021P manufactured by Daicel Co., Ltd.]

TEPIC: Triglycidyl isocyanurate [TEPIC (registered trademark) -L, manufactured by Nissan Chemical Industries, Ltd.]

DOX: Bis((3-ethyl-3-oxetanyl)methyl)ether [Aronoxetane (registered trademark) OXT-221 manufactured by Toa Synthetics Co., Ltd.]

MH700: 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride mixture (molar ratio 70:30) [Ricaced (registered trademark) MH-700 manufactured by Nippon Ewha Co., Ltd.]

PX4ET: Tetrabutylphosphonium O,O-diethylphosphorodithioate [Hycicoline (registered trademark) PX-4ET manufactured by Nippon Chemical Industry Co., Ltd.]

C101A: Diphenyl (4-(phenylthio)phenyl)sulfonium hexafluoroantimonate (V)/50% by mass propylene carbonate solution [CPI (registered trademark) -101A manufactured by San Apro Co., Ltd.]

SI100: Benzyl (4-hydroxyphenyl) (methyl) sulfonium hexafluoroantimonate (V) [Sun Aid SI-100 manufactured by Sanshin Chemical Industry Co., Ltd.]

2EHA: 2-ethylhexanoic acid (Junsei Chemical Co., Ltd.)

NMP: N-methyl-2-pyrrolidone

THF: tetrahydrofuran

[Example 1] Preparation of 2-hexyldecanoate glycidyl (IPGEs)

Into the reaction flask, 30.0 g (117 mmol) of IPA, 17.0 g (141 mmol) of AllBr, 19.4 g (140 mmol) of potassium carbonate, and 300 g of NMP were added. This was stirred at 70°C for 1 hour. The reaction solution was filtered and insoluble matter was removed. 260 g of toluene was added to this filtrate, washed with 300 g of water, and the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 95:5 (volume ratio)) to obtain 33.6 g of allyl 2-hexyldecanoate (IPAEs) as a colorless transparent liquid.

¹ H NMR (300MHz, CDCl ₃ ): δ=5.96~5.86(m,1H),5.34~5.20(m,2H),4.59~4.57(m,2H),2.32(m,1H),1.56~1.26( m,24H),0.88(t,J=7.2Hz,6H)(ppm)

GC-MS(CI): m/z=297(M+1)

Into the reaction flask, 33.2 g (112 mmol) of the IPAEs and 740 g of chloroform were added. To this solution, 55.2 g (224 mmol of pure rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 4 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 95:5 (volume ratio)) to obtain 30.7 g of the target product, glycidyl 2-hexyldecanoate (IPGEs), as a colorless and transparent liquid. The viscosity of the obtained IPGEs was 11 mPa·s (25°C), and the epoxy equivalent weight measured according to JIS K7236:2009 was 315.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.43~4.38(m,1H),3.96~3.90(m,1H),3.21~3.18(m,1H),2.85~2.82(m,1H),2.65~ 2.63(m,1H),2.41~2.35(m,1H),1.60~0.85(m,30H)(ppm)

GC-MS(CI): m/z=313(M+1)

[Example 2] Preparation of 2-octyldecanoate glycidyl (ISTGEs)

Into the reaction flask, 30.0 g (105 mmol) of ISAT, 15.2 g (126 mmol) of AllBr, 17.4 g (126 mmol) of potassium carbonate, and 300 g of NMP were added. This was stirred at 70°C for 3 hours. The reaction solution was filtered and insoluble matter was removed. 260 g of toluene was added to this filtrate, washed with 300 g of water, and the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 95:5 (volume ratio)) to obtain 33.3 g of allyl 2-octyldecanoate (ISTAEs) as a colorless transparent liquid.

¹ H NMR (300MHz, CDCl ₃ ): δ=5.97~5.86(m,1H),5.35~5.21(m,2H),4.60~4.57(m,2H),2.35(m,1H),1.57~1.25( m,28H),0.88(t,J=6.9Hz,6H)(ppm)

GC-MS(CI): m/z=325(M+1)

Into the reaction flask, 32.9 g (101 mmol) of the ISTAEs and 740 g of chloroform were added. To this solution, 62.4 g (253 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 4 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 95:5 (volume ratio)) to obtain 30.0 g of the target product, glycidyl 2-octyldecanoate (ISTGEs), as a colorless and transparent liquid. The obtained ISTGEs had a viscosity of 14 mPa·s (25°C) and an epoxy equivalent weight of 341.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.43~4.38(m,1H),3.96~3.90(m,1H),3.20(m,1H),2.85~2.82(m,1H),2.65~2.63( m,1H),2.38(m,1H),1.57~0.85(m,34H)(ppm)

GC-MS(CI): m/z=341(M+1)

[Example 3] Preparation of 8-methyl-2-(4-methylhexyl)glycidyl decanoate (ISNGEs)

Into the reaction flask, 30.0 g (105 mmol) of ISAN, 15.2 g (126 mmol) of AllBr, 17.4 g (126 mmol) of potassium carbonate, and 300 g of NMP were added. This was stirred at 70°C for 3.5 hours. The reaction solution was filtered and insoluble matter was removed. 260 g of toluene was added to this filtrate, washed with 300 g of water, and the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 95:5 (volume ratio)) to obtain 33.9 g of 8-methyl-2-(4-methylhexyl) allyl decanoate (ISNAEs) as a colorless transparent liquid. .

¹ H NMR (300MHz, CDCl ₃ ): δ=5.99~5.86(m,1H),5.35~5.21(m,2H),4.58(d,J=2.7Hz,2H),2.36(m,1H),1.58 ~0.71(m,34H)(ppm)

GC-MS(CI): m/z=325(M+1)

Into the reaction flask, 33.4 g (103 mmol) of the ISNAEs and 740 g of chloroform were added. To this solution, 48.3 g (253 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 5 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 95:5 (volume ratio)) to obtain 28.4 g of the target product, glycidyl 8-methyl-2-(4-methylhexyl)decanoate (ISNGEs), as colorless. Obtained as a transparent liquid. The obtained ISNGEs had a viscosity of 18 mPa·s (25°C) and an epoxy equivalent weight of 340.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.41(m,1H),3.96~3.89(m,1H),3.22~3.18(m,1H),2.85~2.83(m,1H),2.66~2.64( m,1H),2.54~2.33(m,1H),1.60~0.72(m,34H)(ppm)

GC-MS(CI): m/z=341(M+1)

[Example 4] Preparation of 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanate glycidyl (ISGEs)

Into the reaction flask, 28.4 g (100 mmol) of ISA, 62.5 g (676 mmol) of ECH, and 0.3 g (2.7 mmol) of TMAC were added. This was stirred at 100°C for 2 hours and then cooled to room temperature (approximately 23°C). Here, 25.0 g (mmol) of a 48 mass% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature (approximately 23°C) for 24 hours. To this reaction solution, 20 mL of a 10% by mass aqueous solution of sodium dihydrogen phosphate was added to neutralize the sodium hydroxide. This organic layer was washed with water, and then ECH was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 90:10 (volume ratio)) to obtain the target product, 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid. 30.0 g of glycidyl (ISGEs) was obtained as a colorless and transparent liquid. The obtained ISGEs had a viscosity of 41 mPa·s (25°C) and an epoxy equivalent weight of 334.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.45~4.34(m,1H),4.39~3.94(m,1H),3.20(m,1H),2.86~2.83(m,1H),2.66~2.65( m,1H),2.19(m,1H),1.75~0.88(m,34H)(ppm)

GC-MS(CI): m/z=341(M+1)

[Example 5] Preparation of 5,9-dimethyl-2-(1,5-dimethylhexyl)glycidyl decanoate (IAGEs)

Into the reaction flask, 30.0 g (96 mmol) of IAA, 13.9 g (115 mmol) of AllBr, 21.0 g (152 mmol) of potassium carbonate, and 300 g of NMP were added. This was stirred at 70°C for 1 hour. The reaction solution was filtered and insoluble matter was removed. 260 g of toluene was added to this filtrate, washed with 300 g of water, and the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 95:5 (volume ratio)) to obtain 33.0 g of 5,9-dimethyl-2-(1,5-dimethylhexyl) allyl decanoate (IAAEs) as colorless. Obtained as a transparent liquid.

¹ H NMR (300MHz, CDCl ₃ ): δ=5.97~5.86(m,1H),5.35~5.21(m,2H),4.58(m,2H),2.36(m,1H),1.56~0.73(m, 38H)(ppm)

GC-MS(CI): m/z=353(M+1)

Into the reaction flask, 32.6 g (93 mmol) of the IAAEs and 740 g of chloroform were added. To this solution, 52.4 g (213 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 6 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 95:5 (volume ratio)) to obtain the target product, glycidyl decanoate (IAGEs), 5,9-dimethyl-2-(1,5-dimethylhexyl). 28.4 g was obtained as a colorless transparent liquid. The obtained IAGEs had a viscosity of 32 mPa·s (25°C) and an epoxy equivalent weight of 371.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.40(m,1H),3.95(m,1H),3.19(m,1H),2.85~2.82(m,1H),2.64(m,1H),2.35 (m,1H),0.87~0.75(m,38H)(ppm)

GC-MS(CI): m/z=369(M+1)

[Example 6] Preparation of 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid 4,5-epoxypentyl (ISEPEs)

Into the reaction flask, 30.0 g (105 mmol) of ISA, 10.0 g (116 mmol) of PEO, and 800 g of dichloromethane were added. To this solution, 15.4 g (126 mmol) of DMAP and 24.2 g (126 mmol) of EDC were added while stirring, and stirred at room temperature (approximately 23°C) for 3 days. This reaction solution was washed with 1N hydrochloric acid and 5% by mass saline solution, and then the solvent was distilled off to obtain 5-pentenyl 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid. (ISPEs) were obtained.

The obtained crude product was dissolved in 440 g of chloroform. To this solution, 12.7 g (52 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 5 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 99:1 to 95:5 (volume ratio)) to obtain the target product, 2-(4,4-dimethylpentan-2-yl)-5, 13.1 g of 4,5-epoxypentyl 7,7-trimethyloctanoic acid (ISEPEs) was obtained as a colorless and transparent liquid. The obtained ISEPEs had a viscosity of 44 mPa·s (25°C) and an epoxy equivalent weight of 366.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.11(t,J=6.3Hz,2H),2.95(m,1H),2.76~2.79(m,1H),2.48~2.50(m,1H),2.13 (m,1H),1.84~0.88(m,38H)(ppm)

GC-MS(CI): m/z=369(M+1)

[Example 7] Preparation of 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid 7,8-epoxyoctyl (ISEOEs)

Into the reaction flask, 30.0 g (105 mmol) of ISA, 15.7 g (116 mmol of polished rice) of OEO, and 800 g of dichloromethane were added. To this solution, 15.4 g (126 mmol) of DMAP and 24.2 g (126 mmol) of EDC were added while stirring, and stirred at room temperature (approximately 23°C) for 4 days. This reaction liquid was washed with 1N hydrochloric acid and 5% by mass saline solution, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 95:5 (volume ratio)) to obtain 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid 7-. 33.8 g of octenyl (ISOEs) was obtained as a colorless transparent liquid.

¹ H NMR (300MHz, CDCl ₃ ): δ=5.87~5.73(m,1H),5.02~4.92(m,2H),4.09~4.03(m,2H),2.11~0.82(m,45H)(ppm)

GC-MS(CI): m/z=395(M+1)

Into the reaction flask, 33.3 g (84 mmol) of the ISOEs and 740 g of chloroform were added. To this solution, 27.1 g (110 mmol of polished rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 2 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 99:1 to 95:5 (volume ratio)) to obtain the target product, 2-(4,4-dimethylpentan-2-yl)-5, 20.8 g of 7,8-epoxyoctyl 7,7-trimethyloctanoic acid (ISEOEs) was obtained as a colorless and transparent liquid. The obtained ISEOEs had a viscosity of 51 mPa·s (25°C) and an epoxy equivalent weight of 408.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.07~4.03(m,2H),2.90(m,1H),2.76~2.73(m,1H),2.47~2.45(m,1H),2.11(m, 1H),1.63~0.88(m,44H)(ppm)

GC-MS(CI): m/z=411(M+1)

[Example 8] Preparation of 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid 2-glycidyloxyethyl (ISGEEs)

Into the reaction flask, 30.0 g (105 mmol) of ISA, 11.9 g (117 mmol) of EGMAE, and 400 g of dichloromethane were added. To this solution, 15.5 g (127 mmol) of DMAP and 24.3 g (127 mmol) of EDC were added while stirring, and stirred at room temperature (approximately 23°C) for 4 days. This reaction liquid was washed with 1N hydrochloric acid and 5% by mass saline 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 obtain 2-(4,4-dimethylpentan-2-yl)-5,7, 19.1 g of 2-allyloxyethyl 7-trimethyloctanoic acid (ISAEEs) was obtained as a colorless and transparent liquid.

¹ H NMR (300MHz, CDCl ₃ ): δ=5.94~5.87(m,1H),5.31~5.12(m,2H),4.31~4.17(m,2H),4.03(m,2H),3.65~3.63( m,2H),2.21~2.16(m,1H),1.85~0.83(m,34H)(ppm)

GC-MS(CI): m/z=369(M+1)

Into the reaction flask, 19.0 g (52 mmol) of the ISAEEs and 440 g of chloroform were added. To this solution, 15.6 g (63 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 5 days. To this reaction solution, 200 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 obtain the target product, 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid. 16.9 g of 2-glycidyloxyethyl (ISGEEs) was obtained as a colorless and transparent liquid. The obtained ISGEEs had a viscosity of 47 mPa·s (25°C) and an epoxy equivalent weight of 382.

¹ H NMR (300MHz, CDCl ₃ ): δ=4.24(m,2H),3.81~3.71(m,3H),3.47~3.41(m,1H),3.14(m,1H),2.79(m,1H) ,2.62(m,1H),2.17(m,1H),1.86~0.89(m,34H)(ppm)

GC-MS(CI): m/z=385(M+1)

[Synthesis Example 1] Preparation of 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid 3,4-epoxycyclohexylmethyl (ISECHEs)

Into the reaction flask, 30.0 g (105 mmol) of ISA, 13.0 g (116 mmol) of CHMA, and 800 g of dichloromethane were added. To this solution, 15.4 g (126 mmol) of DMAP and 24.2 g (126 mmol) of EDC were added while stirring, and stirred at room temperature (approximately 23°C) for 2 days. This reaction liquid was washed with 1N hydrochloric acid and 5% by mass saline solution, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 90:10 (volume ratio)) to obtain 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid 3-. 30.0 g of cyclohexenylmethyl (ISCHEs) was obtained as a colorless transparent liquid.

¹ H NMR (300MHz, CDCl ₃ ): δ=5.67(m,2H),4.01~3.97(m,2H),2.15~0.88(m,42H)(ppm)

GC-MS(CI): m/z=379(M+1)

Into the reaction flask, 29.5 g (78 mmol) of the ISCHEs and 740 g of chloroform were added. To this solution, 23.1 g (94 mmol net weight) of mCPBA was added while stirring, and stirred at room temperature (approximately 23°C) for 17 hours. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 95:5 (volume ratio)) to obtain the target product, 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid. 28.4 g of 3,4-epoxycyclohexylmethyl (ISECHEs) was obtained as a colorless and transparent liquid. The obtained ISECHEs had a viscosity of 92 mPa·s (25°C) and an epoxy equivalent weight of 413.

¹ H NMR (300MHz, CDCl ₃ ): δ=3.87~3.83(m,2H),3.17~3.14(m,2H),2.20~0.88(m,42H)(ppm)

GC-MS(CI): m/z=395(M+1)

[Synthesis Example 2] Preparation of 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl=glycidyl=ether (ISGE)

Into the reaction flask, 30.0 g (111 mmol) of ISOL, 24.2 g (200 mmol) of AllBr, 11.3 g (471 mmol) of sodium hydride, and 270 g of THF were added. This was stirred at 70°C for 29 hours. This reaction liquid was washed with 600 g of water, and then the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 95:5 (volume ratio)) to obtain 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl=allyl= 33.4 g of ether (ISAE) was obtained as a colorless and transparent liquid.

¹ H NMR (400MHz, CDCl ₃ ): δ=5.97~5.87(m,1H),5.30~5.24(m,1H),5.18~5.14(m,1H),3.96~3.37(m,1H),3.37~ 3.22(m,2H),1.82~1.71(m,1H),1.56~0.83(m,36H)(ppm)

GC-MS(CI): m/z=311(M+1)

Into the reaction flask, 33.1 g (107 mmol) of the ISAE and 440 g of chloroform were added. To this solution, 52.5 g (213 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 3 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 obtain the target product, 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl= 30.5 g of glycidyl=ether (ISGE) was obtained as a colorless and transparent liquid. The obtained ISGEEs had a viscosity of 18 mPa·s (25°C) and an epoxy equivalent weight of 366.

¹ H NMR (400MHz, CDCl ₃ ): δ=3.67~3.64(m,1H),3.41~3.23(m,3H),3.13(m,1H),2.80~2.77(m,1H),2.61~2.59( m,1H),1.80~0.82(m,35H)(ppm)

GC-MS(CI): m/z=327(M+1)

[Synthesis Example 3] Preparation of glycidyl palmitate (PGEs)

Into the reaction flask, 30.0 g (96 mmol) of PA, 17.0 g (141 mmol) of AllBr, 19.3 g (140 mmol) of potassium carbonate, and 300 g of NMP were added. This was stirred at 70°C for 1 hour. The reaction solution was filtered and insoluble matter was removed. 260 g of toluene was added to this filtrate, and after washing with 300 g of water, the solvent was distilled off. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 90:10 (volume ratio)) to obtain 34.4 g of allyl palmitate (PAEs) as a white solid.

¹ H NMR (400MHz, CDCl ₃ ): δ=5.96~5.89(m,1H),5.34~5.22(m,2H),4.59~4.57(m,2H),2.33(t,J=7.6Hz,2H) ,1.65~1.61(m,2H),1.32~1.25(m,24H),0.88(t,J=6.8Hz,3H)(ppm)

GC-MS(CI): m/z=297(M+1)

Into the reaction flask, 34.1 g (115 mmol) of the PAEs and 440 g of chloroform were added. To this solution, 56.6 g (230 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 4 days. To this reaction solution, 300 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 obtain 29.8 g of the target product, glycidyl palmitate (PGEs), as a white solid. The obtained PGEs had a melting point of 47°C and an epoxy equivalent weight of 309.

¹ H NMR (400MHz, CDCl ₃ ): δ=4.44~4.40(m,1H),3.94~3.89(m,1H),3.23~3.19(m,1H),2.86~2.84(m,1H),2.66~ 2.64(m,1H),2.35(t,J=7.6Hz,2H),1.66~1.62(m,2H),1.33~1.25(m,24H),0.90~0.86(m,3H)(ppm)

GC-MS(CI): m/z=313(M+1)

[Synthesis Example 4] Preparation of 14-methylpentadecanoic acid glycidyl (ωIPGEs)

Into the reaction flask, 295 mg (1.2 mmol) of ωIPA, 167 mg (1.4 mmol) of AllBr, 191 mg (1.4 mmol) of potassium carbonate, and 5 g of NMP were added. This was stirred at 70°C for 4 hours. The reaction solution was filtered and insoluble matter was removed. 26 g of toluene was added to this filtrate, washed with 30 g of water, and the solvent was distilled off to obtain a crude product of allyl 14-methylpentadecanoate (ωIPAEs).

The obtained crude product was dissolved in 7 g of chloroform. To this solution, 536 mg (2.2 mmol of net rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 2 days. To this reaction solution, 10 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 95:5 (volume ratio)) to obtain 258 mg of the target product, glycidyl 14-methylpentadecanoate (ωIPGEs), as a white solid. The obtained ωIPGEs had a melting point of 39°C and an epoxy equivalent weight of 316.

¹ H NMR (400MHz, CDCl ₃ ): δ=4.44~4.40(m,1H),3.93~3.89(m,1H),3.23~3.19(m,1H),2.86~2.84(m,1H),2.66~ 2.64(m,1H),2.37~2.33(m,2H),1.65~1.14(m,23H),0.87~0.85(m,6H)(ppm)

GC-MS(CI): m/z=313(M+1)

[Synthesis Example 5] Preparation of 16-methylheptadecanoic acid glycidyl (ωISGEs)

Into the reaction flask, 275 mg (1.0 mmol) of ωISA, 140 mg (1.2 mmol) of AllBr, 160 mg (1.2 mmol) of potassium carbonate, and 5 g of NMP were added. This was stirred at 70°C for 2 hours. The reaction solution was filtered and insoluble matter was removed. 26 g of toluene was added to this filtrate, washed with 30 g of water, and the solvent was distilled off to obtain a crude product of 14-methylpentadecanoate allyl (ωISAEs).

The obtained crude product was dissolved in 7 g of chloroform. To this solution, 861 mg (3.5 mmol of pure rice) was added while stirring, and stirred at room temperature (approximately 23°C) for 2 days. To this reaction solution, 10 mL of 10 mass% sodium thiosulfate aqueous solution was added to decompose mCPBA. This organic layer was washed with a 5% by 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 = 95:5 (volume ratio)) to obtain 235 mg of the target product, glycidyl 16-methylheptadecanoate (ωISGEs), as a white solid. The melting point of the obtained ωISGEs was 47°C and the epoxy equivalent weight was 334.

¹ H NMR (400MHz, CDCl ₃ ): δ=4.44~4.40(m,1H),3.94~3.89(m,1H),3.22~3.20(m,1H),2.86~2.84(m,1H),2.66~ 2.64(m,1H),2.37~2.33(m,2H),1.65~1.14(m,27H),0.87~0.85(m,6H)(ppm)

GC-MS(CI): m/z=341(M+1)

[Example 9, Comparative Example 1] Compatibility and volatility with Bis-A type epoxy resin

For each epoxy compound (reactive diluent) listed in Table 1, compatibility with BPA, a bisphenol A type epoxy resin, was evaluated.

Each epoxy compound was mixed with BPA so that the concentration was 10% by mass, and an epoxy resin composition was prepared. After stirring this for 5 minutes at room temperature (approximately 23°C), the mixing state was visually confirmed and evaluated according to the following standards. Additionally, for commercially available products, the viscosity of this composition at 25°C was measured. The results are shown together in Table 1.

Furthermore, as an evaluation of volatility, the 5% weight loss temperature (Td _5% ) of each epoxy compound is shown in Table 1.

[Commercial evaluation criteria]

A: Transparent by uniformly mixing

B: Slightly cloudy

C: Insoluble matter is present and solid and liquid are separated.

[Table 1]

As shown in Table 1, the epoxy compound (reactive diluent) used in the present invention was compatible with BPA, a general-purpose epoxy resin. In addition, while BPA has a viscosity of about 12,000 mPa·s, the resin composition of the present invention, in which BPA is mixed with an epoxy compound at 10% by mass, has a viscosity lowered to 2,000 to 6,200 mPa·s. Additionally, it was confirmed that the epoxy compound used in the present invention has a very high 5% weight loss temperature and low volatility.

On the other hand, even if the number of carbon atoms of the -CR ¹ R ² R ³ group is the same, epoxy compounds in which R ¹ and R ² are not each alkyl groups with 2 or more carbon atoms are not compatible with BPA. In addition, the epoxy compound in which R ¹ and R ² each have an alkyl contribution of 2 or more carbon atoms and the -CR ¹ R ² R ³ group has 7 carbon atoms had a very low 5% weight loss temperature and high volatility.

From the above, it was suggested that the epoxy compound used in the present invention can be used as an excellent reactive diluent.

[Examples 10 to 17, Comparative Examples 2 to 4] Production of cured product

To 100 parts by mass of the epoxy resin composition shown in Table 2, MH700 as a curing agent was added in an equimolar amount to the epoxy group of the epoxy compound, and 1 part by mass of PX4ET as a curing accelerator 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 11.

Each composition was sandwiched between two glass substrates previously subjected to release treatment with Optool (registered trademark) DSX (manufactured by Daikin Kogyo Co., Ltd.) along with a U-shaped silicone rubber spacer with a thickness of 3 mm. This was heated in an oven at 100°C for 2 hours (pre-curing), and then the temperature was raised to 150°C and heated for 5 hours (main curing). After slow cooling, the glass substrate was removed to obtain each cured product with a thickness of 3 mm.

The obtained cured product was evaluated for water absorption, relative dielectric constant, and glass transition point (Tg). Meanwhile, each physical property value was measured in the following order. The results are shown together in Table 2.

[Absorption rate]

Measurement was made according to JIS K-6911:2006. Specifically, first, as a pretreatment, the test piece was dried in a glass container maintained at 50°C in an oil bath for 24 hours. This test piece is cooled to 20°C in a desiccator, and its mass (W ₁ [g]) is measured. Next, this test piece was immersed in boiled distilled water for 100 hours, then taken out, cooled in running water at 20°C for 30 minutes, the moisture was wiped off, and the mass after absorption (W ₂ [g]) was immediately measured. From these values, the water absorption rate was calculated using the following equation.

Absorption rate [%]=(W ₂ -W ₁ )÷W ₁ ×100

[relative permittivity]

The capacitance Cp when a voltage of 1 V, 1 MHz was applied to the test piece sandwiched between the electrodes of the holder was measured, and divided by the capacitance C ₀ of air measured under the same conditions to calculate the relative dielectric constant ε _r . In addition, the reduction rate with respect to the relative dielectric constant ε _r0 of the cured product obtained from the composition to which no reactive diluent was added was calculated using the following equation.

Reduction rate [%]=(ε _r0 -ε _r )÷ε _r0 ×100

[Glass transition point]

The TMA of the test piece was measured, a tangent line was drawn on the curve before and after the obtained TMA curve, and Tg was determined from the intersection of the tangent lines.

[Table 2]

As shown in Table 2, it was confirmed that the relative dielectric constant of the epoxy resin composition of the present invention (Examples 10 to 17) was significantly reduced compared to the case where the reactive diluent was not contained (Comparative Example 4). On the other hand, the epoxy resin composition containing a conventionally known reactive diluent had a low reduction rate in relative dielectric constant (Comparative Examples 2 and 3).

[Examples 18-21, Comparative Example 5] Production of cured product

To 100 parts by mass of the epoxy resin composition shown in Table 3, MH700 was added as a curing agent in an equimolar amount to the epoxy group of the epoxy compound. This mixture was mixed by stirring at 90°C for 30 minutes and then cooled to room temperature (approximately 23°C). 1 part by mass of PX4ET was added here as a curing accelerator. This mixture was degassed by stirring at room temperature (approximately 23°C) for 5 minutes to prepare curable compositions 12 to 16.

A cured product with a thickness of 3 mm was produced and evaluated in the same manner as in Example 10, except that each of the obtained compositions was used. The results are shown together in Table 3.

[Table 3]

As shown in Table 3, it was confirmed that the relative dielectric constant and water absorption were significantly reduced in the epoxy resin composition of the present invention (Examples 18 to 21) compared to the case that did not contain a reactive diluent (Comparative Example 5).

[Examples 22, 23, Comparative Examples 6 to 8] Production of thermal cation cured product

To 100 parts by mass of the epoxy resin composition shown in Table 4, 1 part by mass of SI100 previously dissolved in 1 part by mass of propylene carbonate as a thermal acid generator was added. This mixture was stirred and degassed (2,000 rpm for 4 minutes, then again at 1,000 rpm for 4 minutes) to prepare curable compositions 17 to 21.

Each composition was sandwiched between two glass substrates previously subjected to release treatment with Optool (registered trademark) DSX (manufactured by Daikin Kogyo Co., Ltd.) along with a 200-μm-thick silicone rubber spacer. This was heated on a hot plate at 100°C for 1 hour (pre-curing), and then the temperature was raised to 150°C and heated for 1 hour (main curing). After slow cooling, the glass substrate was removed to obtain each cured product with a thickness of 200 μm.

The relative dielectric constant of the obtained cured product was evaluated in the same manner as in Example 10. The results are shown together in Table 4.

[Table 4]

As shown in Table 4, it was confirmed that the relative dielectric constant of the epoxy resin composition of the present invention (Examples 22 and 23) was significantly reduced compared to the case where the reactive diluent was not contained (Comparative Example 8). On the other hand, the epoxy resin composition containing a conventionally known reactive diluent had a low reduction rate in relative dielectric constant (Comparative Examples 6 and 7).

[Examples 24, 25, Comparative Examples 9 to 11] Production of photocationic cured product

To 100 parts by mass of the epoxy resin composition shown in Table 5, 1 part by mass of C101A (effective ingredient conversion) was added as a photoacid generator. This mixture was stirred and degassed (2,000 rpm for 4 minutes, then 1,000 rpm for 4 minutes) to prepare curable compositions 22 to 26.

Each composition was sandwiched between two quartz glass substrates previously subjected to release treatment with Optool (registered trademark) DSX (manufactured by Daikin Kogyo Co., Ltd.) along with a 200-μm-thick silicone rubber spacer. This embedded composition was exposed to UV light for 150 seconds at an illuminance of 20 mW/cm ² (wavelength 365 nm) in an air atmosphere, and then heated on a hot plate at 100°C for 1 hour (post-cure). After slow cooling, the quartz glass substrate was removed to obtain each cured product with a thickness of 200 μm.

The relative dielectric constant of the obtained cured product was evaluated in the same manner as in Example 10. The results are shown together in Table 5.

[Table 5]

As shown in Table 5, it was confirmed that the relative dielectric constant of the epoxy resin composition of the present invention (Examples 24 and 25) was significantly reduced compared to the case where the reactive diluent was not contained (Comparative Example 11). On the other hand, the epoxy resin composition containing a conventionally known reactive diluent had a low reduction rate in relative dielectric constant (Comparative Examples 9 and 10).

[Reference Examples 1 to 3] Reactivity evaluation

For ISGEs, ISECHEs and ISGE, the amounts of 2EHA and xylene shown in Table 6 were mixed and stirred at 140°C for 8 hours. The conversion rate of the epoxy group in each reaction mixture was measured by GC. The results are shown in Table 6.

[Table 6]

As shown in Table 6, the epoxy moiety is an epoxyethyl group (when it contains a group represented by the above formula [2]) rather than a 3,4-epoxycyclohexyl group (when it contains a group shown by the above formula [3]). ) is more reactive (Reference Examples 1 and 2), and it was confirmed that, as for

Claims (18)

An epoxy resin composition comprising at least one epoxy compound represented by formula [1] and an epoxy resin having at least two epoxy groups in the molecule.

(Wherein, R ¹ represents a 3,5,5-trimethylhexyl group, R ² represents a 4,4-dimethylpentan-2-yl group, R ³ represents a hydrogen atom, and =O)O- (where * represents a stage bonded to the -CR ¹ R ² R ³ group), L represents a methylene group, and E represents a group represented by formula [2].)

(In the formula, R ⁴ to R ⁶ represent a hydrogen atom.) delete delete delete delete delete delete A curable composition comprising (a) the epoxy resin composition according to claim 1, and (b) a curing agent. According to clause 8,
A curable composition wherein the curing agent (b) is at least one selected from the group consisting of acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, and polymercaptans. According to clause 8 or 9,
A curable composition comprising 0.5 to 1.5 equivalents of the curing agent (b) based on 1 equivalent of the epoxy group of the (a) epoxy resin composition. A curable composition comprising (a) the epoxy resin composition according to claim 1, and (c) a curing catalyst consisting of (c1) an acid generator and/or (c2) a base generator. According to clause 11,
A curable composition wherein the curing catalyst (c) is an acid generator (c1). According to clause 12,
A curable composition wherein the (c1) acid generator is at least one selected from the group consisting of photoacid generators and thermal acid generators. According to clause 13,
A curable composition wherein the (c1) acid generator is an onium salt. According to clause 14,
A curable composition wherein the (c1) acid generator is a sulfonium salt or an iodonium salt. According to any one of claims 12 to 15,
A curable composition comprising 0.1 to 20 parts by mass of the acid generator (c1) based on 100 parts by mass of the epoxy resin composition (a). A method of using at least one type of epoxy compound represented by formula [1] as a reactive diluent in an epoxy resin composition.

(Wherein, R ¹ represents a 3,5,5-trimethylhexyl group, R ² represents a 4,4-dimethylpentan-2-yl group, R ³ represents a hydrogen atom, and =O)O- (where * represents a stage bonded to the -CR ¹ R ² R ³ group), L represents a methylene group, and E represents a group represented by formula [2].)

(In the formula, R ⁴ to R ⁶ represent a hydrogen atom.) Epoxy compound represented by formula [1a].

(Wherein, R ¹ represents a 3,5,5-trimethylhexyl group, R ² represents a 4,4-dimethylpentan-2-yl group, R ³ represents a hydrogen atom, and R ⁴ to R ⁶ represent hydrogen represents an atom, and L represents a methylene group.)