JP2010090329A - One-pack thermosetting epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-pack thermosetting epoxy resin composition excellent in storage stability. <P>SOLUTION: This one-pack thermosetting epoxy resin composition is provided by containing (A) an epoxy resin, (B) a thiol compound containing two or more mercapto groups in its molecule and (C) a clathration compound in which an imidazole compound and/or an amine-based compound are clathrated by a tetrakisphenol-based compound expressed by formula (I) [wherein, R<SP>1</SP>to R<SP>8</SP>are each H, alkyl, phenyl which may be substituted, halogen or alkoxy]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a one-component thermosetting epoxy resin composition.

  Conventionally, a composition in which a thiol compound and an imidazole compound are used in combination as a curing agent for an epoxy resin has been proposed. A composition in which a thiol compound and an imidazole compound are used in combination as a curing agent for an epoxy resin is excellent in low-temperature curability.

However, the present inventors have found that when a thiol compound and an imidazole compound are used as a curing agent for an epoxy resin to form a one-component composition, such a composition has a problem of poor storage stability. It was.
Then, an object of this invention is to provide the one-pack type thermosetting epoxy resin composition which is excellent in storage stability.

  As a result of diligent research to solve the above problems, the present inventor has found that an epoxy resin (A), a thiol compound (B) having two or more mercapto groups in the molecule, and a tetrakisphenol type represented by a specific formula A one-component thermosetting epoxy resin composition containing an inclusion compound (C) in which an imidazole compound and / or an amine compound is included by a compound is found to have excellent storage stability, and the present invention is completed. I let you.

That is, this invention provides the following 1-3.
1. An imidazole compound and / or an amine compound is included by the epoxy resin (A), the thiol compound (B) having two or more mercapto groups in the molecule, and the tetrakisphenol compound represented by the following formula (I). A one-component thermosetting epoxy resin composition comprising an inclusion body (C).
(Wherein R ^{1 to} R ⁸ each represent a hydrogen atom, an alkyl group, an optionally substituted phenyl group, a halogen atom or an alkoxy group.)
2. The imidazole compound is 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl-2-methylimidazole, 1-methylimidazole, 2-propyl The above is at least one selected from the group consisting of imidazole, imidazole, 1-propylimidazole, 1-butylimidazole, 4-phenylimidazole, 4-methylimidazole, 2-phenylimidazole and 4-hydroxymethyl-2-phenylimidazole The one-component thermosetting epoxy resin composition according to 1.
3. The ratio of the mercapto group to the epoxy group of the epoxy resin (A) (number of moles of the mercapto group / number of moles of the epoxy group) is 0.5 to 1.2, and the clathrate (C) The one-component thermosetting epoxy resin composition according to 1 or 2, wherein the amount of is 1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin (A).

  The one-component thermosetting epoxy resin composition of the present invention is excellent in storage stability.

The present invention will be described in detail below.
The one-component thermosetting epoxy resin composition of the present invention is
An imidazole compound and / or an amine compound is included by the epoxy resin (A), the thiol compound (B) having two or more mercapto groups in the molecule, and the tetrakisphenol compound represented by the following formula (I). It is the one-component thermosetting epoxy resin composition containing the inclusion body (C).
(Wherein R ^{1 to} R ⁸ each represent a hydrogen atom, an alkyl group, an optionally substituted phenyl group, a halogen atom or an alkoxy group.)
The one-component thermosetting epoxy resin composition of the present invention may be hereinafter 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 an average of 2 or more epoxy groups in one molecule. For example, polyglycidyl ether obtained by reacting polychlorophenol such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcinol, polyhydric alcohol such as glycerin and polyethylene glycol and epichlorohydrin; p-hydroxybenzoic acid, Glycidyl ether ester obtained by reacting a hydroxycarboxylic acid such as β-hydroxynaphthoic acid with epichlorohydrin; a polyglycol obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin Glycidyl ester; epoxidized phenol novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, cycloaliphatic epoxy resin, dicyclopentadiene type epoxy resin, 4,4 diaminodiphenyl meta And m- aminophenol such as glycidyl amine type epoxy resins obtained from naphthalene type epoxy resins, biphenyl type epoxy resins, urethane modified epoxy resins.
The epoxy resin (A) is excellent in storage stability, can be a cured product having a high glass transition temperature, and is bisphenol A, dicyclopentadiene type epoxy resin, 4,4 diaminodiphenylmethane from the viewpoint of excellent curability. A glycidylamine type epoxy resin or naphthalene type epoxy resin obtained from glycidylamine or m-aminophenol is preferred.
An epoxy resin (A) can be used individually or in combination of 2 types or more, respectively.

The thiol compound (B) will be described below.
The thiol compound (B) contained in the composition of the present invention is a compound having two or more mercapto groups (—SH) in the molecule.
In the present invention, the thiol compound (B) is used as a curing agent for the epoxy resin (A).

The number of mercapto groups possessed by one molecule of the thiol compound (B) is 2 to 20 from the viewpoint that it is excellent in storage stability, can be a cured product having a high glass transition temperature, and is excellent in curability. Of these, 3 to 10 are more preferable.
Examples of the thiol compound include mercapto group-containing hydrocarbon compounds having two or more mercapto groups (-SH) in the molecule, and mercapto group-containing silicones having two or more mercapto groups (-SH) in the molecule.

The main chain of the mercapto group-containing silicone having two or more mercapto groups in the molecule is silicone.
In the mercapto group-containing silicone, the mercapto group can be directly bonded to the main chain of the mercapto group-containing silicone. The mercapto group can be bonded to the main chain of the mercapto group-containing silicone via an organic group.

  The organic group through the mercapto group and the main chain of the mercapto group-containing silicone is not particularly limited as long as it is a divalent hydrocarbon group. The divalent hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the divalent hydrocarbon group include an aliphatic hydrocarbon group (the aliphatic hydrocarbon group can include an unsaturated bond) and an alicyclic hydrocarbon group (the alicyclic hydrocarbon group is unsaturated). And an aromatic hydrocarbon group and a hydrocarbon group formed by a combination thereof. Among these, an aliphatic hydrocarbon group is preferable from the viewpoint of excellent curability. Examples of the aliphatic hydrocarbon group include those having 1 to 6 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

  In addition to the mercapto group, the main chain of the mercapto group-containing silicone can have, for example, an alkoxy group such as a methoxy group or an ethoxy group; an alkyl group such as a methyl group or an ethyl group.

Examples of the mercapto group-containing silicone include a compound represented by the following formula (1). The mercapto group-containing silicone is preferably a compound represented by the formula (1) from the viewpoint that it is excellent in storage stability, can be a cured product having a high glass transition temperature, and is excellent in curability.
In the formula, R ¹ is an alkyl group, R is an alkylene group, R ² is an alkyl group or an alkoxy group, R ³ is an alkyl group, and n is an integer of 2 or more.

Examples of the alkyl group include a methyl group and an ethyl group.
Examples of the alkylene group include those having 2 to 6 carbon atoms, and specific examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
Examples of the alkyl group or alkoxy group represented by R ² include a methyl group and a methoxy group. Examples of the alkyl group as R ³ include a methyl group.
n is an integer of 2 or more, and is preferably 5 to 10 from the viewpoint that the glass transition temperature (glass transition point) of the cured product is high, excellent in fast curability, and excellent in storage stability. It is more preferable that

As a compound represented by Formula (1), the compound represented by following formula (2) is mentioned, for example. The compound represented by the formula (1) is preferably a compound represented by the formula (2) from the viewpoint that it is excellent in storage stability, can be a cured product having a high glass transition temperature, and is excellent in curability. .
In the formula, R ¹ is an alkyl group, R ² is an alkyl group or an alkoxy group, R ³ is an alkyl group, and n is an integer of 2 or more. R ¹ , R ² , R ³ , and n are as defined above.
Mercapto group-containing silicones can be used alone or in combination of two or more.

The mercapto group-containing silicone is not particularly limited for its production. For example, it can be produced by condensing a mercapto group-containing alkoxysilane compound.
The mercapto group-containing alkoxysilane compound is a silane compound having at least one mercapto group and at least two alkoxy groups. The mercapto group-containing alkoxysilane compound can have an alkyl group such as a methyl group or an ethyl group in addition to the mercapto group and the alkoxy group.
A mercapto group can be bonded to a silicon atom via an organic group. The organic group is as defined above.

As a mercapto group containing alkoxysilane compound, the compound represented by following formula (3) is mentioned, for example.
In the formula, R ¹ and R ⁴ are each independently an alkyl group, R is an alkylene group, m is 2 or 3, n is 1 or 2, and m + n is 3 or 4.
R ¹ and R are as defined above. Examples of the alkyl group as R ⁴ include a methyl group and an ethyl group.

  Examples of mercapto group-containing alkoxysilane compounds include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltrialkoxysilane such as 3-mercaptopropyltriethoxysilane; 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyl. Examples include 3-mercaptopropylalkyldialkoxysilanes such as diethoxysilane.

The method for condensing the mercapto group-containing alkoxysilane compound is not particularly limited. For example, a method of hydrolyzing and condensing a composition containing at least a mercapto group-containing alkoxysilane compound can be mentioned.
The composition containing at least the mercapto group-containing alkoxysilane compound can contain an alkoxysilane other than the mercapto group-containing alkoxysilane. Alkoxysilanes other than mercapto group-containing alkoxysilanes are not particularly limited. For example, a conventionally well-known thing is mentioned.

The mercapto group-containing hydrocarbon compound having two or more mercapto groups in the molecule can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of the mercapto group-containing hydrocarbon compound having two or more mercapto groups in the molecule include compounds represented by the following formulas (4), (5), (6), (7), and (8). .

In Formula (4), R ¹ is an alkyl group having 1 to 6 carbon atoms, and R ^{2 to} R ⁷ each represents an alkylene group having 1 to 10 carbon atoms.
In formula (5), n is an integer of 1 or more.
In formula (6), R < ¹ > -R < ⁸ > shows a hydrocarbon group (for example, alkylene group), respectively.
In formula (7), R < ¹ > -R < ¹² > shows a hydrocarbon group (for example, alkylene group), respectively.
In formula (8), R < ¹ > -R < ⁶ > shows a hydrocarbon group (for example, alkylene group), respectively.

The hydrocarbon compound having two or more mercapto groups in the molecule is preferably a compound represented by the formula (4) from the viewpoint of excellent storage stability and excellent curability.
In Formula (4), R ¹ is an alkyl group having 1 to 6 carbon atoms, and R ^{2 to} R ⁷ each represents an alkylene group having 1 to 10 carbon atoms.

Examples of the compound represented by the formula (4) include trimethylolpropane tristhioglycolate and trimethylolpropane tristhiopropionate.
The compound represented by the formula (4) is preferably trimethylolpropane tristhioglycolate or trimethylolpropane tristhiopropionate from the viewpoint of excellent storage stability and excellent curability.
The production of the mercapto group-containing hydrocarbon compound having two or more mercapto groups in the molecule is not particularly limited. For example, a conventionally well-known thing is mentioned.

  The amount of the thiol compound (B) is superior in storage stability, can be a cured product having a high glass transition temperature, and has an epoxy group that the epoxy resin (A) has from the viewpoint of excellent curability and low temperature curability. The ratio of the mercapto group of the thiol compound (B) to the number of moles of the mercapto group / the number of moles of the epoxy group is preferably 0.5 to 1.2, and preferably 0.7 to 0.9. Is more preferable.

The inclusion body (C) will be described below.
The clathrate (C) contained in the composition of the present invention is a compound in which an imidazole compound and / or an amine compound is clathrated by a tetrakisphenol compound represented by the following formula (I).
(Wherein R ^{1 to} R ⁸ each represent a hydrogen atom, an alkyl group, an optionally substituted phenyl group, a halogen atom or an alkoxy group.)
In the present invention, the clathrate (C) is used as a curing accelerator.

Examples of the alkyl group include those having 1 to 6 carbon atoms. Specific examples include a methyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-hexyl group.
The phenyl group is an unsubstituted or substituted phenyl group, and examples of the substituent that the phenyl group can have include a halogen atom and an alkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group include those having 1 to 6 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and a t-butoxy group.

  The tetrakisphenol compound used in the production of the clathrate (C) is not particularly limited as long as it is a compound represented by the formula (I). Specifically, for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2, 2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3 5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dibromo-4- Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-di-t-butyl-4- Hydro Ciphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,2,2-tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2- Tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2- Tetrakis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-tert-butyl-5-methyl-4-hydroxyphenyl) ethane 1,1,2,2-tetrakis (3-chloro-5-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl-4-hydroxyphenyl) Examples include ethane and 1,1,2,2-tetrakis [(4-hydroxy-3-phenyl) phenyl] ethane.

Of these, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane is preferable from the viewpoint of superior storage stability.
The tetrakisphenol compounds can be used alone or in combination of two or more.

  The imidazole compound used in the production of the clathrate (C) is not particularly limited as long as it is a compound having an imidazole ring. For example, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 1-propylimidazole, 2-propylimidazole, 1-butylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl -1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimid Sol, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- (2'-undecylimidazolyl-)-ethyl-s-triazine, 2,4 -Diamino-6- [2'-ethyl-4-imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl- s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-Fe Ruimidazole, 4-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2- Phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazo Examples include lithium trimellitate.

Among these, from the viewpoint of excellent low-temperature curability and excellent storage stability, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl- 2-methylimidazole is preferred.
The imidazole compounds can be used alone or in combination of two or more.

Examples of the amine compound used in the production of the clathrate (C) include ethylenediamine, trimethylenediamine, hexamethylenediamine, diethylaminopropylamine, trimethylhexamethylenediamine, alkyl-t-monoamine, 1,4- Aliphatic amines such as diazabicyclo (2,2,2) octane (triethylenediamine), N, N-dimethylcyclohexylamine, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol, piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine , Ethylmorpholine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, N, N-dimethylpiperazine 1,8-diazabicyclo (5,4,0) -7-cycloaliphatic and heterocyclic amines such as undecene and the like.
Of these, 1,8-diazabicyclo [5.4.0] -7-undecene is preferable from the viewpoints of excellent low-temperature curability and excellent storage stability.
The amine compounds can be used alone or in combination of two or more.

  As a combination of a tetrakisphenol compound represented by the formula (I) and an imidazole compound and / or an amine compound, 1,1,2,2-tetrakis (4-hydroxyphenyl) from the viewpoint of superior storage stability. ) Ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane At least one selected from 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl-2-methylimidazole, 1-methylimidazole, 2 -Propylimidazole, imidazole, 1-propylimidazole, 1-butylimidazole, 4-phenylimidazole, 4-methyl Imidazole, 2-phenylimidazole, a combination of at least one selected from the group consisting of 4-hydroxy-2-phenyl imidazole and DBU (diazabicycloundecene) are preferred.

  The amount of the clathrate (C) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of being excellent in storage stability and excellent in low-temperature curability. More preferably, it is 15 parts by mass.

The clathrate (C) is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
The inclusion body (C) will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 is a schematic view schematically illustrating an example of an inclusion body (C).
In FIG. 1, an inclusion body (C) 1 has a tetrakisphenol compound 2 represented by the formula (I) as a host molecule and an imidazole compound and / or an amine compound 3 as a guest.
The tetrakisphenol compound 2 represented by the formula (I) has hydrogen bonds (not shown) between the molecules due to the hydroxy group (not shown) of the tetrakisphenol compound 2 represented by the formula (I). By doing so, crystal lattice vacancies 4 by host molecules are formed. An imidazole compound and / or an amine compound 3 is included in the crystal lattice holes 4.

  The composition of this invention can contain an additive as needed other than an epoxy resin (A), a thiol compound (B), and an inclusion body (C). Examples of the additive include a filler (for example, silica, calcium carbonate, etc.), a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, a thixotropic property imparting agent, and a dispersing agent. .

  The composition of the present invention is not particularly limited for its production. For example, the epoxy resin (A), the thiol compound (B) and the clathrate (C), and the additive that can be used as needed, are mixed uniformly using a stirrer so that It can be manufactured as a mold epoxy resin composition.

The composition of the present invention is thermosetting, and the composition of the present invention can be cured under conditions of 100 to 200 ° C. When the composition of the present invention is heated, the hydrogen bond between the tetrakisphenol compounds represented by formula (I) in the clathrate (C) is dissociated by heating, and the imidazole compound and / or the clathrate (C) is dissociated. Alternatively, the mercapto group of the thiol compound (B) is activated by the effect that the tetrakisphenol compound represented by the formula (I) acts as a catalyst simultaneously with the release of the amine compound, and the thiol compound (B) The composition of the present invention can be cured by reacting with the epoxy resin (A).
Moreover, since the composition of this invention can be hardened | cured at the above temperatures, it is excellent in low temperature curability.

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.

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 composition obtained as follows, storage stability and sclerosis | hardenability were evaluated by the method shown below. The results are shown in Tables 1 and 2.

(1) Storage stability The composition obtained as described below was stored in a thermostatic bath at 25 ° C., and the number of days until the composition was no longer fluid was measured.
(2) Curability
According to the hot plate method of JIS C2161: 1997, the gel time at 150 ° C. and 180 ° C. was measured on a hot plate.

2. Manufacture of a composition The components shown in Table 1 were used in the amounts (parts by mass) shown in the same table, stirred with a stirrer and mixed uniformly to prepare a composition.
In addition, the numerical value in the parenthesis of the thiol compound (B) is an equivalent ratio of the SH group (mercapto group) of the thiol compound (B) to the epoxy group of the epoxy resin (A).

Each component shown in Table 1 is as follows.
Epoxy resin (A) 1: Trade name EP4100E, ADEKA epoxy resin, epoxy equivalent 188 g / mol
Thiol compound (B) 1: Trimethylolpropane tristhioglycolate (TMTG) represented by the following formula, manufactured by Sakai Chemical Co., Ltd.
-Thiol compound (B) 2: Product name Z6062H, manufactured by Toray Dow Corning Co., Ltd., a condensate of mercapto group-containing silane compound represented by the following formula, SH equivalent 139 g / mol
In the formula, n is 6-8.
-Inclusion body (C) 1: trade name TEP-2E4MZ, inclusion hardening accelerator made by Nippon Soda Co., Ltd., 2-ethyl-4-methylimidazole is 1,1,2,2-tetrakis- (4-hydroxyphenyl) A compound represented by the following formula, which is clathrated with ethane
-Inclusion body (C) 2: product name TEP-2MZ, inclusion hardening accelerator made by Nippon Soda Co., Ltd., 2-methylimidazole is included in 1,1,2,2-tetrakis- (4-hydroxyphenyl) ethane Compound * inclusion body (C) 3: trade name TEP-2P4MHZ, inclusion hardening accelerator made by Nippon Soda Co., Ltd., 2-phenyl-4-methyl-5-hydroxymethylimidazole is 1,1,2,2 -Compound clathrated with tetrakis- (4-hydroxyphenyl) ethane-Inclusion body (C) 4: Trade name TEP-1B2MZ, Inclusion hardening accelerator manufactured by Nippon Soda Co., Ltd., 1-benzyl-2-methylimidazole Is a compound which is clathrated with 1,1,2,2-tetrakis- (4-hydroxyphenyl) ethane. Inclusion body (C) 5: trade name TEP-DBU, clathrate hardening accelerator manufactured by Nippon Soda Co., Ltd. Diazabicycloundecene is 1,1,2,2-tetrakis- (4-hydroxyphenyl) Compounds as inclusion ethane

Each component shown in Table 2 is as follows.
-Epoxy resin (A) 1: Same as Table 1-Epoxy resin (A) 2: Trade name YX-4000H, biphenyl type epoxy resin manufactured by Japan Epoxy Resin, epoxy equivalent of 196 g / mol
-Thiol compound (B) 1: Same as Table 1-Phenol novolac resin: Trade name H-1, Phenol novolak resin manufactured by Meiwa Kasei Co., Ltd.-Phenol aralkyl resin: Trade name XL-225, manufactured by Mitsui Toatsu Chemical Co., Ltd.-Imidazole Compound 1: Trade name 2E4MZ, Cure Sole, 2-ethyl-4-methylimidazole manufactured by Shikoku Kasei Co., Ltd. ・ Imidazole Compound 2: Trade name 2MZ, Curazole, 2-methylimidazole manufactured by Shikoku Kasei Co., Inc. (C) 1: No. Same as Table 1

As is apparent from the results shown in Tables 1 and 2, Comparative Examples 1 to 4 which did not contain the inclusion body (C) but contained an imidazole compound instead were inferior in storage stability.
Comparative Examples 5 and 6 which did not contain the thiol compound (B) and contained a phenol resin instead had a long gel time and poor curability.
On the other hand, Examples 1-9 were excellent in storage stability and curability.

FIG. 1 is a schematic view schematically illustrating an example of an inclusion body (C).

Explanation of symbols

1 Inclusion body (C)
2 Tetrakisphenol compound represented by formula (I) 3 Imidazole compound and / or amine compound 4 Crystal lattice vacancies

Claims (3)

An imidazole compound and / or an amine compound is included by the epoxy resin (A), the thiol compound (B) having two or more mercapto groups in the molecule, and the tetrakisphenol compound represented by the following formula (I). A one-component thermosetting epoxy resin composition comprising an inclusion body (C).
(Wherein R ^{1 to} R ⁸ each represent a hydrogen atom, an alkyl group, an optionally substituted phenyl group, a halogen atom or an alkoxy group.)   The imidazole compound is 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl-2-methylimidazole, 1-methylimidazole, 2-propyl It is at least one selected from the group consisting of imidazole, imidazole, 1-propylimidazole, 1-butylimidazole, 4-phenylimidazole, 4-methylimidazole, 2-phenylimidazole and 4-hydroxymethyl-2-phenylimidazole. Item 2. A one-component thermosetting epoxy resin composition according to Item 1.   The ratio of the mercapto group to the epoxy group of the epoxy resin (A) (number of moles of the mercapto group / number of moles of the epoxy group) is 0.5 to 1.2, and the clathrate (C) The one-component thermosetting epoxy resin composition according to claim 1, wherein the amount is 1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin (A).