WO2010026777A1 - Heat-cured epoxy resin composition - Google Patents

Abstract

Provided is a heat-cured epoxy resin composition with excellent curing properties. The heat-cured epoxy resin composition contains an epoxy resin (A), an aromatic polyamine compound (B), and a compound represented by formula (I), and is characterized in that the gelling time is no more than 3 min at 150ºC. (In the formula, R1 and R2 represent a hydrogen atom and an alkyl group, respectively.)

Description

Thermosetting epoxy resin composition

The present invention relates to a thermosetting epoxy resin composition.

A composition using an aromatic diamine compound as a curing agent for an epoxy resin provides a cured product having a high glass transition temperature.
The present applicant has previously proposed Patent Document 1 as a two-component curable resin composition that is excellent in storage stability of the first liquid containing an epoxy resin and has a high curing rate at room temperature or lower.
In addition, an epoxy resin composition containing a curable epoxy resin, a curing agent for epoxy resin, and tris (4-methylphenyl) phosphine triphenylborane has been proposed (see Patent Document 2).
Moreover, when using triphenylphosphine with respect to the phenol-type resin as a hardening | curing agent of an epoxy resin, it is known that the hardening time of a composition will become short.

JP 2007-326906 A JP 2006-290946 A

However, when an aromatic diamine compound is used as a curing agent for an epoxy resin, there is a drawback that the curing time is long under conditions of a curing temperature of 80 to 250 ° C.
Further, the present inventors have found that when triphenylphosphine is used as a curing accelerator with respect to a phenolic resin as a curing agent for an epoxy resin, the curing time cannot be shortened.
Further, an epoxy resin composition using trisphenylphosphine triphenylborane or tris (4-methylphenyl) phosphine triphenylborane as a curing accelerator is compared with phenolic resin as a curing agent for epoxy resin. The inventor of the present application has found that the curing time (gelation time) is long as in the case where is used for phenolic resin as a curing agent for epoxy resin.
Then, an object of this invention is to provide the epoxy resin composition excellent in sclerosis | hardenability.

 
（式中、Ｒ¹、Ｒ²はそれぞれ水素原子、アルキル基を示す。） As a result of diligent research to solve the above-mentioned problems, the present inventor uses a compound represented by the following formula (I) as a curing accelerator for an aromatic diamine compound as a curing agent for an epoxy resin. In particular, the inventors have found that a composition having a short curing time and excellent curability can be obtained, and the present invention has been completed.

(In the formula, R ¹ and R ² each represent a hydrogen atom and an alkyl group.)

 
（式中、Ｒ¹、Ｒ²はそれぞれ水素原子、アルキル基を示す。） That is, the present invention relates to a thermosetting epoxy resin composition containing an epoxy resin (A), an aromatic polyamine compound (B), and a compound represented by the following formula (I). The thermosetting epoxy resin composition is provided within 3 minutes.

(In the formula, R ¹ and R ² each represent a hydrogen atom and an alkyl group.)

The thermosetting epoxy resin composition of the present invention is excellent in curability.

 
（式中、Ｒ¹、Ｒ²はそれぞれ水素原子、アルキル基を示す。）
　以下、本発明の熱硬化性エポキシ樹脂組成物を「本発明の組成物」ということがある。 The present invention will be described in detail below.
The present invention
In the thermosetting epoxy resin composition containing the epoxy resin (A), the aromatic polyamine compound (B), and the compound represented by the following formula (I), the gelation time is 150 ° C. or less within 3 minutes. This is a thermosetting epoxy resin composition.

(In the formula, R ¹ and R ² each represent a hydrogen atom and an alkyl group.)
Hereinafter, the thermosetting epoxy resin composition of the present invention may be referred to as “the composition of the present invention”.

The epoxy resin (A) will be described below.
The epoxy resin (A) contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups. For example, a conventionally well-known thing is mentioned. Specifically, for example, bisphenol A type epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, hydrogenated A biphenol type epoxy resin is mentioned.
An epoxy resin (A) can be used individually or in combination of 2 types or more, respectively.

The aromatic polyamine compound (B) will be described below.
The aromatic polyamine compound (B) contained in the composition of the present invention is a compound in which two or more amino groups are bonded to an aromatic hydrocarbon group.
In the present invention, the aromatic polyamine compound (B) is used as a curing agent. The aromatic polyamine compound (B) can react with the epoxy resin (A).
When the composition of the present invention contains an aromatic thiirane compound (C), the aromatic polyamine compound (B) can react with the epoxy resin (A) and the aromatic thiirane compound (C).
When the composition of the present invention contains an aromatic thiirane compound (C), the aromatic polyamine compound (B) reacts preferentially with the aromatic thiirane compound (C) in the composition of the present invention, and the NH group is removed. Generate. The produced NH group can react with the epoxy resin (A). The amino group which an aromatic polyamine compound (B) has may react with an epoxy resin (A) directly.

 
　式中、Ｒ²は、アルキレン基、芳香族炭化水素基、カルボニル基、フルオレン基、スルホニル基、エーテル基およびスルフィド基からなる群から選ばれる少なくとも１種である。
　アルキレン基としては、例えば、メチレン基、エチレン基が挙げられる。
　Ｒ²は、アルキレン基、芳香族炭化水素基、カルボニル基、フルオレン基、スルホニル基、エーテル基およびスルフィド基からなる群から選ばれる少なくとも２種とすることができる。 The aromatic hydrocarbon group is not particularly limited. The aromatic hydrocarbon group can have a substituent. Examples of the substituent include an alkyl group and an alkoxy group. The aromatic hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
As an aromatic hydrocarbon group, what is represented by a following formula is mentioned, for example.

In the formula, R ² is at least one selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group.
Examples of the alkylene group include a methylene group and an ethylene group.
R ² can be at least two selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group and a sulfide group.

The aromatic polyamine compound (B) is preferably an aromatic diamine compound from the viewpoint of superior curability. An aromatic diamine compound is a compound in which two amino groups are bonded to an aromatic hydrocarbon group.

 
［式（ＩＩ）中、Ｒ³、Ｒ⁴はそれぞれアルキル基であり、Ｒ⁵は、アルキレン基、芳香族炭化水素基、カルボニル基、フルオレン基、スルホニル基、エーテル基およびスルフィド基からなる群から選ばれる少なくとも１種であり、ｍ、ｎはそれぞれ０～４の整数である。］ Examples of the aromatic polyamine compound (B) include those represented by the formula (II). In the formula (II), two amino groups are bonded to the benzene ring.

[In the formula (II), R ³ and R ⁴ are each an alkyl group, and R ⁵ is selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group and a sulfide group. At least one selected, and m and n are each an integer of 0 to 4. ]

The aromatic polyamine compound represented by the formula (II) can have R ³ and R ⁴ as substituents.
Examples of the alkyl group include those having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, and a propyl group are mentioned. The alkyl group is preferably a methyl group or an ethyl group from the viewpoint of excellent storage stability and fast curability.
Examples of the alkylene group include those having 1 to 6 carbon atoms. Examples include a methylene group and an ethylene group. The alkylene group is preferably a methylene group from the viewpoint of excellent storage stability and fast curability.
m and n are each preferably an integer of 0 to 2 from the viewpoint of excellent storage stability and fast curability.
The amino group is preferably para-positioned to R ⁵ from the viewpoint of excellent storage stability and fast curability.
The aromatic hydrocarbon group is not particularly limited as long as it is divalent. The aromatic hydrocarbon group can have a substituent such as a methyl group.
When the aromatic hydrocarbon group and the alkylene group are combined, the combination of the aromatic hydrocarbon and the alkylene group is not particularly limited. For example, the alkylene group which has an aromatic hydrocarbon group is mentioned. Specifically, for example, when two alkylene groups are bonded via an aromatic hydrocarbon, when an aromatic hydrocarbon is bonded as a side chain of the alkylene group, the aromatic hydrocarbon group and the alkylene group are bonded. And the case where an aromatic hydrocarbon group and an alkylene group are respectively bonded to two benzene rings represented by the formula (II). Examples of the aromatic hydrocarbon include a benzene ring and naphthalene. The aromatic hydrocarbon can have a substituent such as a methyl group.

 
　式中、Ｒ²は、アルキレン基、芳香族炭化水素基、カルボニル基、フルオレン基、スルホニル基、エーテル基およびスルフィド基からなる群から選ばれる少なくとも１種である。
　芳香族ポリアミン化合物（Ｂ）は、硬化性により優れ、貯蔵安定性に優れるという観点から、式（４）で表される化合物、メチレンビス（２－エチル６－メチルアニリン）であるのが好ましい。
　なかでも、Ｒ²は、硬化性により優れるという観点から、アルキレン基、カルボニル基、フルオレン基であるのが好ましく、メチレン基、カルボニル基、フルオレン基であるのがより好ましい。
　また、Ｒ²は、本発明の組成物が芳香族チイラン化合物（Ｃ）を含有する場合、硬化性により優れるという観点から、アルキレン基、カルボニル基、フルオレン基であるのが好ましく、メチレン基、カルボニル基であるのがより好ましい。
　芳香族ポリアミン化合物（Ｂ）は、それぞれ単独でまたは２種以上を組み合わせて使用することができる。
　芳香族ポリアミン化合物（Ｂ）はその製造について特に制限されない。芳香族ポリアミン化合物（Ｂ）として市販品を使用することができる。 Examples of the aromatic polyamine compound (B) include a compound represented by the following formula (4) and methylene bis (2-ethyl 6-methylaniline).

In the formula, R ² is at least one selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group.
The aromatic polyamine compound (B) is preferably a compound represented by the formula (4), methylene bis (2-ethyl 6-methylaniline), from the viewpoint of excellent curability and excellent storage stability.
Among these, R ² is preferably an alkylene group, a carbonyl group, or a fluorene group, and more preferably a methylene group, a carbonyl group, or a fluorene group, from the viewpoint of superior curability.
R ² is preferably an alkylene group, a carbonyl group, or a fluorene group from the viewpoint of better curability when the composition of the present invention contains an aromatic thiirane compound (C). More preferably, it is a group.
An aromatic polyamine compound (B) can be used individually or in combination of 2 types or more, respectively.
The aromatic polyamine compound (B) is not particularly limited for its production. A commercial item can be used as an aromatic polyamine compound (B).

The amount of the aromatic polyamine compound (B) is excellent in curability, and from the viewpoint that the glass transition temperature (glass transition point) of the cured product is high, the equivalent number of active hydrogens that the aromatic polyamine compound (B) has is epoxy. The amount of the epoxy group contained in the resin (A) is preferably 0.5 to 2.5 equivalents, more preferably 0.7 to 2.0 equivalents.
The aromatic polyamine compound (B) has an amino group as a group containing active hydrogen. The amino group has two active hydrogens per nitrogen atom.

 
 
　式中、Ｒ¹、Ｒ²はそれぞれ水素原子、アルキル基を示す。
　Ｒ¹は水素原子、アルキル基を示す。Ｒ²は水素原子、アルキル基を示す。
　Ｒ¹、Ｒ²は同じでも異なっていてもよい。複数のＲ¹は同じでも異なっていてもよい。複数のＲ²は同じでも異なっていてもよい。 The compound represented by formula (I) will be described below.
In the composition of the present invention, the compound represented by the formula (I) is a curing accelerator or a curing accelerator (if the composition of the present invention further contains an aromatic thiirane compound (C), ) Is used.
The compound represented by the formula (I) contained in the composition of the present invention has the following structure.

In the formula, R ¹ and R ² represent a hydrogen atom and an alkyl group, respectively.
R ¹ represents a hydrogen atom or an alkyl group. R ² represents a hydrogen atom or an alkyl group.
R ¹ and R ² may be the same or different. A plurality of R ¹ may be the same or different. A plurality of R ² may be the same or different.

 
　式中、Ｐｈはフェニル基またはフェニレン基を示す。なお、式（２）中のＭｅ－Ｐｈ－におけるＰｈはフェニレン基である。
　本発明の組成物は、硬化性により優れ、ガラス転移温度が高くなるという観点から、式（Ｉ）で表される化合物として式（１）で表される化合物および／または式（２）で表される化合物を含有するのが好ましい。 The alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms from the viewpoint of excellent curability and a high glass transition temperature. Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
Examples of the compound represented by the formula (I) include a compound represented by the formula (1) and a compound represented by the formula (2).

In the formula, Ph represents a phenyl group or a phenylene group. In the formula (2), Ph in Me—Ph— is a phenylene group.
The composition of the present invention is superior in curability and has a high glass transition temperature. From the viewpoint of increasing the glass transition temperature, the compound represented by the formula (I) and / or the formula (2) is used. It is preferable to contain the compound.

The compound represented by the formula (1) and the compound represented by the formula (2) will be described below.
In the composition of the present invention, the compound represented by the formula (1) or the compound represented by the formula (2) is a curing accelerator or a curing acceleration assistant (the composition of the present invention further comprises an aromatic thiirane compound (C ) Is used as a curing acceleration aid).

The compound name of the compound represented by the formula (1) is triphenylphosphine triphenylborate, which is sometimes referred to as “TPP-S” in the present specification.
The compound name of the compound represented by the formula (2) is trisparamethylphenylphosphine triphenylborate, which is sometimes referred to as “TPTP-S” in the present specification. In the formula (2), the methyl group can be bonded to any of the ortho, meta and para positions.
The compound represented by the formula (I) is not particularly limited for its production.
The compound represented by the formula (1) is not particularly limited for its production. A commercial item can be used as a compound represented by Formula (1). The same applies to the compound represented by the formula (2).
The compounds represented by formula (I) can be used alone or in combination of two or more.

The amount of the compound represented by the formula (I) is 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of excellent curability and high glass transition temperature of the cured product. It is preferably 3 to 10 parts by mass.

In the present invention, from the viewpoint of excellent curability and a high glass transition temperature of the cured product, the number of active hydrogen equivalents of the aromatic polyamine compound (B) is based on the epoxy group of the epoxy resin (A). The amount of the compound represented by the formula (I) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A).

The microcapsule will be described below.
In the composition of the present invention, either or both of the compound represented by the formula (I) and the aromatic polyamine compound are contained as microcapsules encapsulated by a thermoplastic resin. A one-component composition that is superior in storage stability while maintaining rapid curability can be obtained.
In the present invention, the microcapsule has one or both of the compound represented by the formula (I) and the aromatic polyamine compound as a core, and has a thermoplastic resin as a shell.
The compound represented by the formula (I) or the aromatic polyamine compound is a solid (or a melting point exceeding 70 ° C.) at 25 to 70 ° C. from the viewpoint of easy microencapsulation when producing microcapsules. preferable. The core of the microcapsule is preferably a compound represented by the formula (I) or an aromatic diamine from the viewpoint of easy microencapsulation.
When both the compound represented by the formula (I) and the aromatic polyamine compound are contained as microcapsules encapsulated by a thermoplastic resin, the composition of the present invention contains the compound represented by the formula (I) A microcapsule encapsulated with a thermoplastic resin and a microcapsule encapsulated with a thermoplastic resin of an aromatic polyamine compound can be contained. Further, the compound represented by the formula (I) and the aromatic polyamine compound may be encapsulated in one microcapsule.

The thermoplastic resin used as the shell is not particularly limited. For example, urethane resin; styrene butadiene elastomer; polyvinyl acetal resin; phenoxy resin; polymethyl methacrylate resin; polyvinyl alcohol; (meth) acrylic monomers such as acrylic acid ester, itaconic acid ester, crotonic acid ester, etc. Monofunctional compounds such as 1 to 8 alkyl ethers and those in which part or all of the hydrogen atoms of the alkyl group of this alkyl ester are substituted with allyl groups, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, etc. Monomer obtained from polyfunctional monomers such as ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, bisphenol A di (meth) acrylate, and methylenebis (meth) acrylamide Chromatography, and the like.
The thermoplastic resins can be used alone or in combination of two or more.

Among these, urethane resins, styrene butadiene elastomers, polyvinyls are preferred from the viewpoints of excellent storage stability and fast curability, excellent film-forming properties and mechanical strength, and the ability to maintain the glass transition temperature of the obtained cured product. It is preferably at least one selected from the group consisting of an acetal resin, polyvinyl alcohol and phenoxy resin.

The urethane resin is not particularly limited as long as it is a compound having a urethane bond. For example, those obtained by reaction of polyisocyanates and polyamines, those obtained by reaction of polyisocyanates and water, those obtained by reaction of polyisocyanates and polyhydric alcohols, Examples thereof include those obtained by reaction of isocyanates, polyvalent amines and polyhydric alcohols.

The polyvalent isocyanate used in producing the urethane resin may be a compound having two or more isocyanate groups in the molecule. Specifically, for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate Aromatic polyisocyanates such as xylylene-1,4-diisocyanate and polyisocyanates having an isocyanate group bonded to an alkylene group having an aromatic hydrocarbon group; trimethylene diisocyanate, hexamethylene diisocyanate, Aliphatic polyisocyanates such as pyrene-1,2-diisocyanate, butylene-1,2-diisocyanate, lysine isocyanate; cycloaliphatic polyisocyanates such as cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate Isocyanate; adduct of hexamethylene diisocyanate and hexanetriol, adduct of 2,4-tolylene diisocyanate and prenzcatechol, adduct of tolylene diisocyanate and hexanetriol, adduct of tolylene diisocyanate and trimethylolpropane And an adduct of xylylene diisocyanate and trimethylolpropane and an adduct of hexamethylene diisocyanate and trimethylolpropane.

Among them, from the viewpoints of excellent storage stability and fast curability, excellent film forming properties and mechanical strength, aromatic poly- ylene such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and the like. Isocyanates are preferred.
Polyvalent isocyanates can be used alone or in combination of two or more.

The polyvalent amine used when producing the urethane resin may be a compound having two or more amino groups in the molecule. Specifically, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine; o-phenylene Aromatic polyamines such as diamine, m-phenylenediamine, and p-phenylenediamine; amino groups on alkylene groups having an aromatic hydrocarbon group such as o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine And alicyclic polyamines such as menthanediamine, bis (4-amino-3-methylcyclohexyl) methane, isophoronediamine and 1,3-diaminocyclohexane; spiroacetal diamines.
Polyvalent amines can be used alone or in combination of two or more.

The polyhydric alcohol used when using the urethane resin may be aliphatic, aromatic or alicyclic. For example, catechol, resorcinol, 1,2-dihydroxy-4-methylbenzene, 1,3-dihydroxy-5-methylbenzene, 3,4-dihydroxy-1-methylbenzene, 3,5-dihydroxy-1-methylbenzene, 2,4-dihydroxyethylbenzene, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,7-naphthalenediol, 2,3-naphthalenediol, o, o'-biphenol, p, p'-biphenol, bisphenol A, bis- (2-hydroxyphenyl) methane, xylylenediol, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,1 1-trimethylolpropane, hexanetriol, pentaerythritol, glycerin, and sorbitol.
Polyhydric alcohols can be used alone or in combination of two or more.

The styrene butadiene elastomer is not particularly limited. For example, a conventionally well-known thing is mentioned.
The weight average molecular weight of the styrene butadiene elastomer is preferably 12,000 to 50,000 from the viewpoint of excellent storage stability and fast curability.
In the present invention, the weight average molecular weight is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

The polyvinyl acetal resin is not particularly limited. Examples thereof include polyvinyl formal resin and polyvinyl butyral resin.
The weight average molecular weight of the polyvinyl acetal resin is preferably 10,000 to 60,000 from the viewpoint of excellent storage stability and fast curability.

Polyvinyl alcohol is not particularly limited. For example, a conventionally well-known thing is mentioned. The weight average molecular weight of polyvinyl alcohol is preferably 10,000 to 150,000 from the viewpoint of excellent storage stability and fast curability.

Phenoxy resin is not particularly limited. For example, it is a high molecular weight epoxy resin having a molecular weight of 10,000 or more selected from bisphenol A and / or bisphenol F.

The microcapsule is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
Each of the microcapsules can be used alone or in combination of two or more.
Among these, a microcapsule that encapsulates the compound represented by the formula (I) is preferable from the viewpoint of excellent storage stability and fast curability.
Also, from the viewpoint of excellent storage stability and fast curability, and excellent film-forming properties and mechanical strength, the shell material is selected from the group consisting of urethane resin, styrene butadiene elastomer, polyvinyl acetal resin, polyvinyl alcohol and phenoxy resin. Preferred are microcapsules containing at least one selected from the above.

In the present invention, when the microcapsule having the compound represented by the formula (I) is contained as a core, the aromatic polyamine compound may be microencapsulated or may not be microencapsulated.
Moreover, when the microcapsule which has an aromatic polyamine compound as a core is contained, the compound represented by Formula (I) may be microencapsulated or may not be microencapsulated.

The thermoplastic resin in the microcapsule is an epoxy resin, which can maintain the glass transition temperature of the resulting cured product, is superior in storage stability and fast curability, and is excellent in film forming properties and mechanical strength. The total content is preferably 1 to 20% by mass.

The average particle diameter (diameter) of the microcapsules is preferably 0.1 to 50 (unit: micron) from the viewpoint of excellent storage stability and fast curability. In the present invention, the average particle size is measured using a particle size distribution analyzer SALD-7100 (manufactured by Shimadzu Corporation).
The thickness of the shell in the microcapsule is preferably 0.01 to 10 (unit: micron) from the viewpoints of excellent storage stability and fast curability, and excellent film forming properties and mechanical strength. In the present invention, the thickness of the shell is measured using a particle size distribution analyzer SALD-7100 (manufactured by Shimadzu Corporation).

The composition of the present invention can further contain an aromatic thiirane compound (C).
The aromatic thiirane compound (C) that can be contained in the composition of the present invention is an aromatic hydrocarbon compound having a thiirane group and an aromatic hydrocarbon group.
In the present invention, the aromatic thiirane compound (C) is used as a curing accelerator. In the present invention, the aromatic thiirane compound (C) can be used in place of a part of the aromatic polyamine compound (B).
The aromatic thiirane compound (C) reacts with the aromatic polyamine compound (B) to generate an SH group. The generated SH group can react with the epoxy resin (A).

The aromatic hydrocarbon group that the aromatic thiirane compound (C) has is not particularly limited. For example, a phenyl group and a naphthyl group are mentioned. The aromatic hydrocarbon group can have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a cycloalkyl group, and an aryl group. The aromatic hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
In the aromatic thiirane compound (C), the thiirane group and the aromatic hydrocarbon group can be bonded via an organic group.
The organic group is a hydrocarbon group that can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The hydrocarbon group is not particularly limited.
Examples of the organic group include —O—CH ₂ —, —O—CH ₂ —CH═CH—, and —O—CO—CH ₂ —.

From the viewpoint that the amount of the aromatic thiirane compound (C) is more excellent in curability, the equivalent number of SH groups generated from the aromatic thiirane compound (C) is based on the epoxy group of the epoxy resin (A). It is preferably 0.3 to 1.0, and more preferably 0.4 to 0.7.

The composition of the present invention includes an epoxy resin (A), an aromatic polyamine compound (B), a compound represented by the formula (I), and an aromatic thiirane compound (C) that can be used as necessary. If necessary, an additive can be further contained.
The composition of the present invention is represented by the epoxy resin (A), the aromatic polyamine compound (B), the aromatic thiirane compound (C), and the compound represented by the formula (1) and / or the formula (2). In addition to the compound, an additive can be further contained as necessary.
Examples of the additive include a curing agent other than the aromatic polyamine compound (B), a filler (filler), a reactive diluent, a plasticizer, a thixotropic agent, a pigment, a dye, an anti-aging agent, an antioxidant, Examples thereof include an antistatic agent, a flame retardant, an adhesiveness imparting agent, a dispersant, and a solvent.

Examples of the thermosetting epoxy resin composition of the present invention include a one-component thermosetting epoxy resin composition and a two-component thermosetting epoxy resin composition. In the present invention, “one-component thermosetting epoxy resin composition” may be described as “one-component type”, and “two-component thermosetting epoxy resin composition” may be described as “two-component type”. .
The composition of the present invention is not particularly limited for its production. For example, the epoxy resin (A), the aromatic polyamine compound (B), the compound represented by the formula (I), and the additive are sufficiently kneaded using a stirring device such as a mixing mixer under reduced pressure or in a nitrogen atmosphere. By uniformly dispersing, the composition of the present invention can be produced as a one-component composition.
Further, for example, the epoxy resin (A), the aromatic polyamine compound (B), the compound represented by the formula (1) and / or the compound represented by the formula (2), and can be used as necessary. The composition of the present invention can be produced as a one-component composition by sufficiently kneading and uniformly dispersing the additive under a reduced pressure or in a nitrogen atmosphere using a stirring device such as a mixing mixer.

The composition of the present invention is not particularly limited in its production even when the compound represented by formula (I) and / or the curing agent is encapsulated by microcapsules. When the microcapsule encapsulates the compound represented by the formula (I), for example, an epoxy resin, a microcapsule encapsulating the compound represented by the formula (I), a curing agent, and an addition that can be used as necessary The composition of the present invention can be produced as a one-component composition by sufficiently mixing the agent under a reduced pressure or under a nitrogen atmosphere using a stirring device such as a mixing mixer. Further, when the microcapsule encapsulates the curing agent, for example, the epoxy resin, the compound represented by the formula (I), the microcapsule encapsulating the curing agent, and an additive that can be used as necessary under reduced pressure or Under a nitrogen atmosphere, the composition of the present invention can be produced as a one-component composition by sufficiently mixing using a stirring device such as a mixing mixer.

In the case where the composition of the present invention and the compound represented by the formula (I) and / or the curing agent are encapsulated by microcapsules, from the viewpoint of excellent storage stability, the condition is at 25 ° C. with respect to the initial viscosity. The increase rate of the viscosity after leaving for 24 hours can be 10% or less, and is more preferable. The viscosity was measured at 25 ° C. using an E-type viscometer VISCONIC EHD type (manufactured by Toki Sangyo Co., Ltd.).

When the compound represented by formula (I) and / or the curing agent of the composition of the present invention is encapsulated by microcapsules, it has excellent storage stability and can be stored for a long time at room temperature (20 to 30 ° C.). it can.
When the composition of the present invention is a one-pack type, the workability on site is excellent.

When the two-component composition of the present invention is used, the production thereof is not particularly limited. For example, a two-part type having a first liquid (main agent) containing an epoxy resin (A) and a second liquid (curing agent) containing an aromatic polyamine compound (B) and a compound represented by formula (I) It can be manufactured as a composition. The additive can be added to the first liquid and / or the second liquid. The first liquid and the second liquid can be produced by sufficiently kneading and uniformly dispersing using a stirring device such as a mixing mixer under reduced pressure or nitrogen atmosphere.
Further, for example, a first liquid (main agent) containing an epoxy resin (A), an aromatic polyamine compound (B), a compound represented by formula (1) and / or a compound represented by formula (2) The composition of the present invention can be produced as a two-component composition having a second liquid (curing agent) to be contained. The additive can be added to the first liquid and / or the second liquid. The first liquid and the second liquid can be produced by sufficiently kneading and uniformly dispersing using a stirring device such as a mixing mixer under reduced pressure or nitrogen atmosphere.
When the composition of the present invention is a two-component type, it is preferable from the viewpoint of excellent storage stability.

In the present invention, the gelation time (gel time) of the thermosetting epoxy resin composition is 3 minutes (180 seconds) at 150 ° C. The gel time is preferably within 60 seconds at 150 ° C., more preferably within 50 seconds.
In the present invention, the gel time (gel time) was measured by a method according to JIS C2161: 1997 or a method using a Yasuda gel time tester.

The composition of the present invention can be used, for example, for adhesives, paints, civil engineering and construction, electricity, transportation equipment, medical use, packaging use, textile use, and sports / leisure use.
Examples of the adherend to which the composition of the present invention can be applied include metal, glass, plastic, mortar, concrete, rubber, wood, leather, cloth, and paper.
The method for applying the composition of the present invention to the adherend is not particularly limited. For example, a conventionally well-known thing is mentioned.

The temperature at which the composition of the present invention is cured is preferably from 100 to 250 ° C., more preferably from 120 to 200 ° C., from the viewpoints of excellent curability and high glass transition temperature of the cured product. .

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

1. Evaluation About the epoxy resin composition obtained as follows, gel time and glass transition temperature were evaluated by the method shown below. The results are shown in Tables 1 and 2.
(1) Gel time Evaluation of curability measured the gel time at 150 degreeC using the Yasuda-type gel time tester (No.153 gel time tester by Yasuda Seiki Seisakusyo Co., Ltd.).
The Yasuda-type gel time tester is a device that rotates a rotor in a test tube containing a sample in an oil bath, and when the gelation proceeds and a certain torque is applied, the rotor is dropped by a magnetic coupling mechanism and the timer is stopped.
(2) Glass transition temperature The epoxy resin composition obtained as described below was cured in an oven at 150 ° C. for 1 hour, and the cured product was subjected to dynamic viscoelasticity measurement (Dynamic Mechanical Analysis) with a strain of 0.01% and a frequency of 10 Hz. Then, the storage elastic modulus (G ′) was measured by performing forced elongation excitation in the temperature range from room temperature to 200 ° C. under the condition of a temperature rising rate of 5 ° C./min.

2. Production of Epoxy Resin Composition The components shown in Tables 1 and 2 below were mixed in the amounts (parts by mass) shown in the same table to produce an epoxy resin composition.

 

 

 

 

 
　・芳香族ポリアミン化合物（Ｂ）３：下記式で表されるビス（アミノフェニル）フルオレン、JFEケミカル株式会社製

 
　・芳香族ポリアミン化合物（Ｂ）４：下記式で表されるメチレンビス（２－エチル６－メチルアニリン）（商品名カヤハードＭＥＤ、イハラケミカル工業株式会社製）

 
　・式（Ｉ）で表される化合物１：下記式（１）で表される化合物、北興化学工業株式会社製

 
　・式（Ｉ）で表される化合物２：下記式（２）で表される化合物、北興化学工業株式会社製

 
　・ＴＰＰ：東京化成工業株式会社製、硬化促進助剤として使用
　・脂肪族アミン：下記式で表される化合物、商品名DMP-30、東京化成工業株式会社社製

 
　・アミン系潜在性硬化剤：ＰＮ２３Ｊ（味の素ファインテクノ株式会社製）
　・フェノールノボラック樹脂硬化剤：ＭＥＨ－８０００Ｈ（明和化成株式会社製）
　・フェノールアラルキル樹脂硬化剤：ＭＥＨ－７８００Ｓ（明和化成株式会社製）
　・酸無水物硬化剤：リカシッドＭＴ－５００（新日本理化株式会社製） Details of each component shown in Tables 1 and 2 are as follows.
・ Epoxy resin (A): EP4100E (made by ADEKA) Bisphenol A type epoxy resin Epoxy equivalent 188g / mol
Aromatic polyamine compound (B) 1: Compound represented by the following formula, manufactured by Tokyo Chemical Industry Co., Ltd.

Aromatic polyamine compound (B) 3: bis (aminophenyl) fluorene represented by the following formula, manufactured by JFE Chemical Co., Ltd.

Aromatic polyamine compound (B) 4: Methylenebis (2-ethyl6-methylaniline) represented by the following formula (trade name: Kayahard MED, manufactured by Ihara Chemical Industry Co., Ltd.)

-Compound represented by formula (I) 1: Compound represented by formula (1) below, manufactured by Hokuko Chemical Co., Ltd.

Compound 2 represented by formula (I): Compound represented by formula (2) below, manufactured by Hokuko Chemical Co., Ltd.

-TPP: manufactured by Tokyo Chemical Industry Co., Ltd., used as a curing accelerator.-Aliphatic amine: a compound represented by the following formula, trade name: DMP-30, manufactured by Tokyo Chemical Industry Co., Ltd.

・ Amine-based latent curing agent: PN23J (Ajinomoto Fine Techno Co., Ltd.)
・ Phenol novolac resin curing agent: MEH-8000H (Maywa Kasei Co., Ltd.)
・ Phenol aralkyl resin curing agent: MEH-7800S (Maywa Kasei Co., Ltd.)
・ Acid anhydride curing agent: Ricacid MT-500 (manufactured by Shin Nippon Chemical Co., Ltd.)

As is apparent from the results shown in Tables 1 and 2, Comparative Example I-1, which does not contain the compound represented by formula (I), has a gel time at 150 ° C. of more than 3 minutes and poor curability, resulting in a glass transition. The temperature was low. In Comparative Example I-5 not containing the compound represented by the formula (I), the gel time at 150 ° C. exceeded 3 minutes and the curability was poor. In addition, Comparative Examples I-2 to 4 which do not contain the compound represented by the formula (I) and contain another curing accelerator (TPP, aliphatic amine, amine-based latent curing agent) have a gel time at 150 ° C. Over 3 minutes, the curability was poor and the glass transition temperature was low. In Comparative Examples I-6 to 8 which do not contain the compound represented by the formula (I) and contain another curing accelerator (TPP, aliphatic amine, amine-based latent curing agent), the gel time at 150 ° C. is 3 minutes. And the curability was poor. In Comparative Example I-9 using triphenylphosphine with respect to the phenolic resin as a curing agent for the epoxy resin, the gel time at 150 ° C. exceeded 3 minutes and the curability was poor. Further, Comparative Examples I-10 to 11 containing a compound represented by the formula (I) but containing a phenolic resin curing agent (combination of the compound represented by the formula (I) and the phenolic resin) In Comparative Example I-12 containing an acid anhydride curing agent, the gel time at 150 ° C. exceeded 3 minutes as in Comparative Example I-9, and the curability was poor.
On the other hand, Examples I-1 to 13 had a gel time at 150 ° C. within 120 seconds, had excellent curability, and had a high glass transition temperature. Specifically, Examples I-1 to 13 can be cured under the conditions of 120 to 200 ° C. despite having an aromatic polyamine, and the curing time is short. That is, the thermosetting epoxy resin composition of the present invention is excellent in low-temperature curability as compared with a conventional epoxy resin composition containing an epoxy resin and an aromatic polyamine.
3. Evaluation About the composition obtained as follows, gel time, a viscosity, and a viscosity increase rate were evaluated with the following method. The results are shown in Tables 3-7.
(1) Gel time (fast curing)
For evaluation of curability, gel time at 150 ° C. was measured on a hot plate in accordance with JIS C2161: 1997. Specifically, 0.1 g of the epoxy resin composition obtained as described below was placed on a hot plate, and a metal bar was stirred at a rate of 60 ± 5 times / minute, and the composition became a gel from the start of evaluation ( The time until the entire mixture could not be stirred or the needle tip did not stick) was defined as the gel time (gel time).

(2) Viscosity The initial viscosity of the composition obtained as described below was measured under the condition of 25 ° C. using an E-type viscometer VISCONIC EHD type (manufactured by Toki Sangyo Co., Ltd.).
In addition, the composition obtained as described below was stored in a thermostatic bath at 25 ° C. for 24 hours, and then the viscosity of the composition (viscosity after storage) was measured in the same manner as the initial viscosity.
(3) Viscosity increase rate (storage stability)
The viscosity increase rate was calculated by fitting the obtained initial viscosity and the viscosity value after storage to the following formula.
Viscosity increase rate (%) = (viscosity after storage−initial viscosity) / initial viscosity × 100
As a criterion for evaluating the rate of increase in viscosity, when it was within 10%, it could be used as a one-component thermosetting epoxy resin composition.

4). Microencapsulation of the compound represented by the formula (I) (production of microcapsules having the compound represented by the formula (I) as a core)
Microencapsulation was performed by a spray drying method using a spray dryer GS310 manufactured by Yamato Scientific Co., Ltd.
(1) Microcapsules having a thickness corresponding to 10% by mass of the core weight TPP-S (10 g, melting point 205 ° C., manufactured by Hokuko Chemical Co., Ltd., the same shall apply hereinafter) (or TPTP-S: 10 g, melting point 171 ℃, made by Hokuko Chemical Co., Ltd., the same shall apply hereinafter)) in a solvent: ethyl acetate (40 g), a curing accelerator solution 50 g, and a solvent: a thermoplastic resin solution (solvent) in ethyl acetate (9 g) Medium thermoplastic resin (1 g) was mixed and spray-dried using the above spray-drying device to obtain a powder (microcapsule having a thickness of 10% by mass).
(2) A hardening accelerator solution in which microcapsules TPP-S (10 g) (or TPTP-S: 10 g) having a thickness corresponding to 20% by mass of the weight of the core are suspended in a solvent: ethyl acetate (40 g) 50 g and a thermoplastic resin solution (2 g of thermoplastic resin in a solvent) dissolved in a solvent: ethyl acetate (18 g) are mixed and spray-dried using the above spray-drying apparatus to obtain a powder (20% by weight thickness). Microcapsules).

(1) TPP-S @ MC1
Shelling agent: Microencapsulation was performed so that urethane resin Desmocol 500 (manufactured by Bayer Holding Co., Ltd., the same applies hereinafter) had a thickness of 10% by mass with respect to the core (TPP-S). The obtained microcapsule is designated as TPP-S @ MC1. The average particle size of TPP-S @ MC1 was 10 μm.

(2) TPP-S @ MC2
Shell agent: Microencapsulation was performed so that the urethane resin Desmocol 500 had a thickness of 20 mass% with respect to the core (TPP-S). The obtained microcapsule is designated as TPP-S @ MC2. The average particle size of TPP-S @ MC2 was 11 μm.

(3) TPP-S @ MC3
Microencapsulation was performed so that the shell agent: styrene butadiene elastomer / tuffprene 912 (manufactured by Asahi Kasei Co., Ltd., block copolymer, hereinafter the same) had a thickness of 10% by mass with respect to the core (TPP-S). The obtained microcapsule is designated as TPP-S @ MC3. The average particle size of TPP-S @ MC3 was 10 μm.

(4) TPP-S @ MC4
Shell agent: Polyvinyl acetal resin KS10 (manufactured by Sekisui Chemical Co., Ltd., weight average molecular weight 56,000, hydroxy group 18 mol%, acetalization degree 80 mol%, the same applies hereinafter) is 10 with respect to the core (TPP-S). Microencapsulation was performed so as to obtain a thickness of mass%. The obtained microcapsule is designated as TPP-S @ MC4. The average particle size of TPP-S @ MC4 was 10 μm.

(5) TPP-S @ MC5
Shell agent: phenoxy resin YP-50 (manufactured by Tohto Kasei Co., Ltd., weight average molecular weight 60,000 to 80,000, the same shall apply hereinafter) is microscopic so that the thickness of the core (TPP-S) is 10 mass% Encapsulation was performed. The obtained microcapsule is designated as TPP-S @ MC5. The average particle size of TPP-S @ MC5 was 10 μm.

(6) TPP-S @ MC6
Shell agent: Microencapsulation was performed so that polyvinyl alcohol (trade name NH-18, manufactured by Nippon Synthetic Chemical Co., Ltd.) had a thickness of 10% by mass with respect to the core (TPP-S). The obtained microcapsule is designated as TPP-S @ MC6. The average particle size of TPP-S @ MC6 was 10 μm.

(7) TPTP-S @ MC1
Shell agent: Microencapsulation was performed so that the phenoxy resin YP-50 had a thickness of 10 mass% with respect to the core (TPTP-S). The obtained microcapsule is designated as TPTP-S @ MC1. The average particle size of TPTP-S @ MC1 was 10 μm.

5). Microencapsulation of curing agent (Manufacture of microcapsules with curing agent as core)
(1) Curing agent (1) @ MC1
Shell agent: urethane resin Desmocol 500 is the core [curing agent (1): compound represented by the following formula, melting point 89 ° C., manufactured by Tokyo Chemical Industry Co., Ltd., and so on. The microencapsulation was performed so that the thickness was 10% by mass. Let the obtained microcapsule be hardening | curing agent (1) @ MC1. The average particle of the curing agent (1) @ MC1 was 10 μm.

(2) Curing agent (1) @ MC2
Shell agent: Microencapsulation was performed so that the urethane resin Desmocol 500 had a thickness of 20 mass% with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening | curing agent (1) @ MC2. The average particle of the curing agent (1) @ MC2 was 10 μm.

(3) Curing agent (1) @ MC3
Shell agent: Microencapsulation was carried out so that the thickness of styrene butadiene elastomer / tuffprene 912 was 10% by mass with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening | curing agent (1) @ MC3. The average particle of the curing agent (1) @ MC3 was 10 μm.

(4) Curing agent (1) @ MC4
Shell agent: Microencapsulation was performed so that the polyvinyl acetal resin KS10 had a thickness of 10% by mass with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening | curing agent (1) @ MC4. The average particle of the curing agent (1) @ MC4 was 10 μm.

(5) Curing agent (1) @ MC5
Shell agent: Microencapsulation was performed so that the phenoxy resin YP-50 had a thickness of 10% by mass with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening | curing agent (1) @ MC5. The average particle of the curing agent (1) @ MC5 was 10 μm.

 
　得られたマイクロカプセルを硬化剤（２）＠ＭＣ１とする。硬化剤（２）＠ＭＣ１の平均粒子は10μｍであった。 (6) Curing agent (2) @ MC1
Shell agent: phenoxy resin YP-50 has a thickness of 10% by mass with respect to the core [curing agent (2): bis (aminophenyl, melting point: 237 ° C.) fluorene represented by the following formula, manufactured by JFE Chemical Co., Ltd.]. Microencapsulation was performed as described above.

Let the obtained microcapsule be hardening | curing agent (2) @ MC1. The average particle of the curing agent (2) @ MC1 was 10 μm.

6). Production of Compositions Compositions were produced by using the components shown in Tables 3 to 7 in the amounts (parts by mass) shown in the same table and mixing them with a vacuum stirrer.
In Tables 3, 4 and 6, the numerical value having “eq” as a unit with respect to the amount of the curing agent is the number of equivalents of active hydrogen of the curing agent to the epoxy group (active hydrogen / epoxy group). .
In Tables 3 and 4, the microcapsules encapsulating the compound represented by formula (I) indicate the amount (parts by mass) as microcapsules.
In Table 5, about the microcapsule which encloses a hardening | curing agent, the quantity (mass part) as a microcapsule is shown.

 

 

 

 

 

 

 

 

 

 

 
　・硬化剤（４）：下記式で表されるメルカプトシラン縮合物（Ｚ６３６２Ｈ、東レダウ製）

 
　式中ｎは６～８である。
　・硬化剤（５）：商品名ＰＮ、フェノールノボラック（日本化薬株式会社製）
　・硬化剤（６）：商品名ＸＹＬＯＫ－４Ｌ、キシリレングリコール/フェノール縮合物（三井化学株式会社製）
　・硬化剤（７）：下記式で表されるメチレンビス（２－エチル６－メチルアニリン）（商品名カヤハードＭＥＤ、イハラケミカル工業株式会社製）

 
　・ＴＰＰ－Ｓ＠ＭＣ１～ＴＰＰ－Ｓ＠ＭＣ６、ＴＰＴＰ－Ｓ＠ＭＣ１：上記のとおり製造した、式（Ｉ）で表される化合物を内包するマイクロカプセル
　・硬化剤（１）＠ＭＣ１～硬化剤（１）＠ＭＣ５、硬化剤（２）＠ＭＣ１：上記のとおり製造した、硬化剤を内包するマイクロカプセル
　・ＴＰＰ－Ｓ：第１表の式（Ｉ）で表される化合物１と同様
　・ＴＰＴＰ－Ｓ：第１表の式（Ｉ）で表される化合物２と同様
　・フェノールノボラック樹脂硬化剤：第２表と同様
　・フェノールアラルキル樹脂硬化剤：第２表と同様
　・酸無水物硬化剤：第２表と同様
　・ＴＰＰ：第２表と同様
　・脂肪族アミン：第２表と同様
　・アミン系潜在性硬化剤：第２表と同様 The components shown in Tables 3 to 7 are as follows.
-Epoxy resin: as in Table 1-Curing agent (1): similar to the aromatic polyamine compound (B) 1 in Table 1-Curing agent (2): with the aromatic polyamine compound (B) 3 in Table 1 Similarly ・ Curing agent (3): TMTG represented by the following formula: Trimethylolpropane tristhioglycolate, manufactured by Sakai Chemical Co., Ltd.

Curing agent (4): Mercaptosilane condensate represented by the following formula (Z6362H, manufactured by Toray Dow)

In the formula, n is 6 to 8.
Curing agent (5): Trade name PN, phenol novolak (manufactured by Nippon Kayaku Co., Ltd.)
Curing agent (6): trade name XYLOK-4L, xylylene glycol / phenol condensate (Mitsui Chemicals)
Curing agent (7): Methylenebis (2-ethyl6-methylaniline) represented by the following formula (trade name: Kayahard MED, manufactured by Ihara Chemical Industry Co., Ltd.)

TPP-S @ MC1 to TPP-S @ MC6, TPTP-S @ MC1: Microcapsules containing the compound represented by the formula (I) produced as described above Curing agent (1) @ MC1 to curing agent (1) @ MC5, curing agent (2) @ MC1: microcapsules encapsulating the curing agent, prepared as described above • TPP-S: the same as compound 1 represented by formula (I) in Table 1 • TPTP -S: Same as compound 2 represented by formula (I) in Table 1 -Phenol novolak resin curing agent: Same as Table 2 -Phenol aralkyl resin curing agent: Same as Table 2 -Acid anhydride curing agent: Same as Table 2. TPP: Same as Table 2. Aliphatic amine: Same as Table 2. Amine-based latent curing agent: Same as Table 2.

As apparent from the results shown in Table 3 to Table 7, the epoxy resin, the compound represented by the formula (I), and the curing agent containing an aromatic polyamine represented by the formula (II), Examples IV-1 to 6 in which the compound represented by the formula (I) and the curing agent were not encapsulated by the thermoplastic resin were excellent in rapid curability. Comparative Examples III-5 and 6 which did not contain the aromatic polyamine represented by the formula (II) but instead contained a phenol resin or a phenol resin condensate were inferior in rapid curability.
In addition, Comparative Examples IV-1 to IV-8 containing no compound represented by the formula (I) were inferior in rapid curability. Comparative Example IV-9 containing a phenol resin as a curing agent and TPP as a curing accelerator, and containing a phenol resin instead of an aromatic polyamine represented by the formula (II) as a curing agent Comparative Examples IV-10 to 12 containing TPP-S as inferior in rapid curability.
On the other hand, Examples II-1 to 15 and Examples III-1 to 12 had a viscosity increase rate of 10% or less, excellent storage stability, and could maintain excellent rapid curability. .

Claims (5)

In the thermosetting epoxy resin composition containing the epoxy resin (A), the aromatic polyamine compound (B), and the compound represented by the following formula (I), the gelation time is 150 ° C. or less within 3 minutes. The thermosetting epoxy resin composition characterized by the above-mentioned.

(Wherein R ¹ and R ² represent a hydrogen atom and an alkyl group, respectively) The thermosetting epoxy resin composition according to claim 1, comprising a compound represented by the following formula (1) and / or a compound represented by the following formula (2) as the compound represented by the formula (I). object.

(In the formula, Ph represents a phenyl group or a phenylene group.) The thermosetting epoxy resin composition according to claim 1 or 2, wherein the aromatic polyamine compound (B) is represented by the following formula (II).

[In the formula (II), R ³ and R ⁴ are each an alkyl group, and R ⁵ is selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group and a sulfide group. At least one selected, and m and n are each an integer of 0 to 4. ] Any one or both of the compound represented by the formula (I) and the aromatic polyamine compound (B) are contained as microcapsules encapsulated by a thermoplastic resin. The thermosetting epoxy resin composition described in 1. The number of equivalents of active hydrogen that the aromatic polyamine compound (B) has is 0.5 to 2.5 equivalents relative to the epoxy group that the epoxy resin (A) has,
The thermosetting epoxy resin according to any one of claims 1 to 4, wherein the amount of the compound represented by the formula (I) is 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A). Composition.