JP6233930B2 - Novel inclusion compound, epoxy resin composition containing the same, and cured product thereof - Google Patents

Description

  The present invention relates to a novel clathrate compound, particularly to a novel clathrate compound useful as a curing agent or a curing accelerator such as an epoxy resin, and further relates to an epoxy resin composition containing the novel clathrate compound and a cured product thereof.

The clathrate compound is a compound in which a guest compound is clathrated with a host compound, and can stabilize a compound unstable to moisture or the like and can control the elution of the guest compound into the solution. As host compounds, bisphenol compounds, tetrakisphenol compounds, phenylsulfone compounds, aromatic carboxylic acid compounds (Patent Documents 1 to 5, etc.) are known.
On the other hand, epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties. As a curing agent for curing such an epoxy resin, imidazole is used, but the epoxy resin-imidazole mixed liquid has a quick start of curing, and thickens and gels in long-term storage. Has a problem that it cannot be used.
Therefore, as a curing agent, an imidazolic acid addition salt obtained by adding hydroxybenzoic acid to imidazole (Patent Document 6) or a tetrakisphenol compound (for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane) is used. (Hereinafter referred to as TEP)) and the use of an inclusion compound of imidazole (Patent Documents 7 and 8) have been proposed. The present inventors have also proposed a cured resin composition using an inclusion compound of an isophthalic acid compound and imidazole (Patent Document 9). However, although these have certain effects, they are still not satisfactory.

  As will be described later, a curing agent containing a novolak phenol compound similar to the host compound of the clathrate compound of the present invention and 2-ethyl-4-methylimidazole is known, but both form clathrate compounds. It has been confirmed that this is not done (Patent Documents 10 to 13). Non-Patent Documents 1 and 2 describe inclusion compounds of compounds encompassed by the formula (I) of the present invention. Examples of guest compounds include solvent-based compounds such as toluene, cyclohexane, and ethanol. However, imidazole compounds and similar compounds are not exemplified.

JP-A-6-166646 JP-A-1-190602 Japanese Patent Laid-Open No. 62-22701 JP 61-53201 A JP 2001-172225 A Japanese Patent Publication No.4-2638 JP-A-11-71449 Japanese Patent Laid-Open No. 10-324826 International Patent Publication WO2008 / 074427 Pamphlet JP 56-59841 A JP 60-40125 A JP 2002-20683 A US Pat. No. 3,493,630 Bull. Chem. Soc. Jpn., 62, 1111-1116 (1989) Bull. Chem. Soc. Jpn., 66, 828-835 (1993)

  In view of the above technical background, an object of the present invention is to provide a novel inclusion compound having an imidazole compound as a guest compound.

  As a result of intensive studies to solve the above problems, the present inventors have found that a tri- or tetramer of a cresol compound forms an inclusion compound with 2-ethyl-4-methylimidazole, and completes the present invention. It came to.

That is, the present invention
(1) Formula (I)
(In the formula, R is a hydroxy group, a nitro group, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a hydroxy group, a C6-C10 aryl group, a C6-C10 aryl C1-C10 alkyl group, A C1-C10 acyl group, a C1-C10 alkoxycarbonyl group, a carboxyl group, a cyano group, or a carbamoyl group, m represents an integer of 0 or 1-3, and a represents 1 or 2.) And a clathrate compound containing 2-ethyl-4-methylimidazole.

The present invention also provides:
(2) It relates to an epoxy resin composition containing the following components (A) and (B).
(A) Epoxy resin (B) Formula (I)

(In the formula, R is a hydroxy group, a nitro group, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a hydroxy group, a C6-C10 aryl group, a C6-C10 aryl C1-C10 alkyl group, A C1-C10 acyl group, a C1-C10 alkoxycarbonyl group, a carboxyl group, a cyano group, or a carbamoyl group, m represents an integer of 0 or 1-3, and a represents 1 or 2.) An inclusion compound containing 2-ethyl-4-methylimidazole and

Furthermore, the present invention provides
(3) It is related with the hardened | cured material obtained by hardening the epoxy resin composition as described in said (2).

  The clathrate compound of the present invention is useful as a curing agent or curing accelerator for epoxy resins.

FIG. 4 is a diagram showing ¹ H-NMR measurement results of inclusion compound A obtained in Synthesis Example 1. It is a figure which shows the measurement result of the powder X-ray diffraction (XRD) of the clathrate compound A obtained by the synthesis example 1. It is a figure which shows the measurement result of the thermogravimetry (TG) -differential scanning calorimetry (DSC) of the clathrate compound A obtained by the synthesis example 1. FIG. It is a figure which shows the measurement result of ¹ H-NMR of the clathrate compound B obtained by the synthesis example 3. It is a figure which shows the measurement result of XRD of the inclusion compound B obtained by the synthesis example 3. FIG. It is a figure which shows the measurement result of TG-DSC of the inclusion compound B obtained by the synthesis example 3. FIG. It is a figure which shows the measurement result of DSC of the epoxy resin composition A. It is a figure which shows the measurement result of DSC of the epoxy resin composition B. It is a figure which shows the measurement result of DSC of the epoxy resin composition C. It is a figure which shows the measurement result of DSC of the epoxy resin composition D. It is a figure which shows the measurement result of DSC of the epoxy resin composition A. It is a figure which shows the measurement result of DSC of the epoxy resin composition B. It is a figure which shows the measurement result of DSC of the epoxy resin composition C. It is a figure which shows the measurement result of DSC of the epoxy resin composition D. It is a figure which shows the measurement result of TG-DSC of the mixture obtained by the reference example.

(New inclusion compound)
The inclusion compound of the present invention has the formula (I)

(In the formula, R is a hydroxy group, a nitro group, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a hydroxy group, a C6-C10 aryl group, a C6-C10 aryl C1-C10 alkyl group, A C1-C10 acyl group, a C1-C10 alkoxycarbonyl group, a carboxyl group, a cyano group, or a carbamoyl group, m represents an integer of 0 or 1-3, and a represents 1 or 2.) As a host compound, 2-ethyl-4-methylimidazole as a guest compound.
Here, “inclusion compound” refers to a compound in which two or more molecules are bound by a weak bond other than a covalent bond, and more preferably, two or three or more molecules are weak other than a covalent bond. A crystalline compound bonded by bonding. A compound to be included is called a host compound, and a compound to be included is called a guest compound.

Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
As C1-C10 alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl Group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, octyl group, nonyl group, A decyl group etc. are mentioned.
Examples of the C3-C10 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopropylmethyl group.

  The C1-C10 alkyl group substituted with a hydroxy group can be exemplified by a C1-C10 alkyl group having one or more hydroxy groups, specifically, a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxy Ethyl group, 3-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 1-hydroxy-n-propyl group, 2,3-dihydroxy-n-propyl group, 2-hydroxy-2-propyl group, Examples thereof include a 4-hydroxy-n-butyl group and a 2-hydroxy-1,1-dimethyl-ethyl group.

A C6-C10 aryl group means a monocyclic or polycyclic aryl group. Here, in the case of a polycyclic aryl group, a partially saturated group is included in addition to the fully unsaturated group. Examples thereof include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
The C6-C10 aryl C1-C10 alkyl group is a group in which the C6-C10 aryl group and the C1-C10 alkyl group are bonded to each other, and includes a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, and a 1-phenyl-n group. -Hexyl group, naphthalen-1-ylmethyl group, naphthalen-2-ylethyl group, 1-naphthalen-2-yl-n-propyl group, inden-1-ylmethyl group and the like can be mentioned.
C1-C10 acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, etc. Is mentioned.
Examples of the C1-C10 alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a t-butoxycarbonyl group, and the like.

(Method for producing inclusion compound)
The inclusion compound of the present invention can be obtained by mixing with the host compound in a solvent.
After the host compound and guest compound are added to the solvent, the mixture is subjected to a heat treatment at room temperature or higher and below the boiling point of the solvent used, with stirring as necessary, and then precipitated, evaporated, or filtered. By doing so, the target clathrate compound can be obtained. The obtained inclusion compound is preferably a crystalline compound. Further, the obtained inclusion compound may contain a third component such as a solvent, and the third component is preferably 40 mol% or less, more preferably 10 mol% or less. Most preferably, it contains no components.

The host compound and / or guest compound is reacted in its entirety or in part in a solvent or preferably in a solvent, but it is preferred that both be completely or partly dissolved in the solvent. When dissolving in a solvent, the entire amount does not need to be dissolved in the solvent, and at least a part of the amount only needs to be dissolved in the solvent. As the solvent, water, methanol, ethanol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile and the like can be used. In particular, it is preferable to mix the solution after dissolving the host compound and the guest compound in the solvent.
The heat treatment is not particularly limited, but it can be heated, for example, within a range of 40 to 120 ° C., and preferably heated to reflux.

  The addition ratio of the host compound and the guest compound is not particularly limited as long as an inclusion compound can be formed, but the guest compound is 0.1 to 5.0 mol with respect to 1 mol of the host compound. It is preferably 0.5 to 3.0 mol.

  The step after heating by dissolving or suspending the host compound and guest compound in a solvent is not particularly limited as long as a solid compound containing the host compound and guest compound as constituent elements can be obtained. The solid compound may be precipitated by stopping the heating, or after the heating is stopped, it is preferably left at a temperature of room temperature to 5 ° C. for 30 minutes to 24 hours. After the solid compound is precipitated, the target clathrate compound is obtained by, for example, filtering and drying. Depending on the type, a crystalline compound can be obtained.

The structure of the clathrate compound obtained can be confirmed by thermal analysis (TG-DSC, etc.), infrared absorption spectrum (IR), X-ray diffraction pattern (XRD), solid NMR spectrum, and the like. The composition of the clathrate compound can be confirmed by thermal analysis, ¹ H-NMR spectrum, high performance liquid chromatography (HPLC), elemental analysis or the like.

(Epoxy resin composition)
The clathrate compound of the present invention can be used, for example, as a curing agent or curing accelerator for an epoxy resin composition. Further, when the inclusion compound is a curing agent, it may further contain a curing accelerator, and when the inclusion catalyst is a curing accelerator, it may further contain a curing agent.

As the epoxy resin, conventionally known various polyepoxy compounds can be used. For example, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, 2,2-bis (hydroxyphenyl) propane diglycidyl ether, 2, 2-bis (4-hydroxy-3,5-dibromophenyl) propane diglycidyl ether, 2,2-bis (4-hydroxyperhydrophenyl) propane diglycidyl ether, bis (4-hydroxyphenyl) sulfone diglycidyl ether, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane diglycidyl ether, 3,5-dimethyl-4-hydroxybiphenyl diglycidyl ether, 1,2-bis (4-Hydroxyphenyl) ethanediglycidylate Bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether, fluoroglycinol triglycidyl ether , Trihydroxybiphenyl triglycidyl ether, 3,4,3 ′, 4′-tetraglycidyloxybenzophenone, bisresorcinol tetraglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, 1,3-bis [1 -(2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2,3-epoxypropoxy) -1 -Trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4′-bis (2,3-epoxypropoxy) octafluorobiphenyl, aromatic glycidyl ether compounds such as phenol novolac bisepoxy compounds,
Alicyclic diepoxy acetal represented by the following formula,
Alicyclic diepoxy adipate represented by the following formula,
An alicyclic diepoxycarboxylate represented by the following formula,
Dicyclopentadiene dioxide represented by the following formula,
Vinylcyclohexene dioxide represented by the following formula,
Cyclohexene oxide glycidyl ether represented by the following formula
Cyclohexene oxide glycidyl ester represented by the following formula
Alicyclic polyepoxy compounds such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3- Dicarboxylate, glycidyl ester compounds such as dimer acid glycidyl ester, diglycidyl aniline, diglycidyl toluidine, triglycidyl aminophenol, tetraglycidyl diaminodiphenylmethane, glycidyl amine compounds such as diglycidyl tribromoaniline, diglycidyl hydantoin, glycidyl glycid Examples include heterocyclic epoxy compounds such as oxyalkylhydantoin and triglycidyl isocyanurate Door can be.

  The amount of the clathrate compound to be used may be the same amount as that of a normal curing agent or curing accelerator, and depends on the curing method. In the case of an addition type curing agent in which a curing agent molecule is always incorporated into a cured resin by reacting with an epoxy group, it is usually included with respect to 1 mol of an epoxy group, depending on the properties of the required resin. The inclusion compound is used so that the curing agent and / or the curing accelerator (guest compound) is about 0.1 to 1.0 mol. In addition, in the case of a polymerization type curing agent or a photoinitiated type curing agent that induces a polymerization addition reaction between oligomers without causing the curing agent molecule to be incorporated into the resin, it is also a curing accelerator. In the case of using as a guest compound, the guest compound in the clathrate compound is preferably contained in an amount of 0.01 to 3.0 mol, more preferably 0.3 to 1.0 mol, relative to 1 mol of the epoxy group. preferable.

  The epoxy resin composition can be manufactured by mixing the epoxy resin and the clathrate compound of the present invention, but usually heated to about 60 to 100 ° C. and mixed so that a sufficient mixed state is formed. . In the production of an epoxy resin, the stability of one liquid at this temperature is important. The method for producing an epoxy curable resin is not particularly limited as long as it is a method of curing the epoxy resin composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 to 250 ° C., Preferably it is 100-200 degreeC, and it is preferable to harden | cure at such temperature for a short time.

  In addition to the aforementioned epoxy resin compositions, plasticizers, organic solvents, reactive diluents, extenders, fillers, reinforcing agents, pigments, flame retardants, thickeners, release agents, etc., as necessary Various additives can be blended. Other additives include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxy. Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane Silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane; Um, light calcium carbonate, natural silica, synthetic silica, fused silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc, mica, wollastonite, potassium titanate, aluminum borate , Sepiolite, Zonotolite, etc .; NBR, polybutadiene, chloroprene rubber, silicone, crosslinked NBR, crosslinked BR, acrylic, core shell acrylic, urethane rubber, polyester elastomer, functional group-containing liquid NBR, liquid polybutadiene, liquid polyester, liquid polysulfide , Elastomer modifiers such as modified silicones and urethane prepolymers;

  Hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyl oxide, bis (pentabromo) phenylethane, tris (tribromophenoxy) Triazine, ethylenebistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, polypentabromobenzyl acrylate, triphenyl phosphate, trigresyl phosphate, trixinyl phosphate, cresyl diphenyl Phosphate, xylyldiphenyl phosphate, cresyl bis (di-2,6-xylenyl) phosphate Fate, 2-ethylhexyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresidyl) phosphate, resorcinol bis (di-2,6-xylenyl) phosphate, tris (chloroethyl) phosphate, Tris (chloropropyl) phosphate, tris (diclopropyl) phosphate, tris (tribromopropyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, anionic oxalic acid treated aluminum hydroxide, nitrate treated Aluminum hydroxide, high-temperature hydrothermal treatment aluminum hydroxide, stannic acid surface treatment hydrated metal compound, nickel compound surface treatment magnesium hydroxide, silicone poly -Flame retardants such as surface treated magnesium hydroxide, procovite, multilayer surface treated hydrated metal compound, cationic polymer treated magnesium hydroxide; high density polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, nylon 6, 6. Engineering plastics such as polyacetal, polyethersulfone, polyetherimide, polybutylene terephthalate, polyetheretherketone, polycarbonate, polysulfone; plasticizer; n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl Diluents such as ether, dicyclopentadiene diepoxide, phenol, cresol, t-butylphenol; extenders; reinforcing agents; colorants; thickeners; higher fatty acids, Higher fatty acid esters, higher fatty acid calcium, and the like, for example, mold release agents such as carnauba wax and polyethylene wax; The blending amount of these additives is not particularly limited, and the blending amount can be appropriately determined within the limit that the effects of the present invention can be obtained.

  Further, the epoxy resin composition may contain other resins in addition to the epoxy resin. Examples of other resins include polyester resins, acrylic resins, silicone resins, polyurethane resins, and the like.

  The epoxy resin composition is suitable for uses such as epoxy resin adhesives, semiconductor encapsulants, laminated boards for printed wiring boards, varnishes, powder paints, casting materials, inks, etc., for curing epoxy resins. Can be used.

Examples are shown below, but the technical scope of the present invention is not limited by these Examples.
[Synthesis of inclusion compounds]
(Synthesis Example 1)
2.16 g (9 mmol) of 2,6-bis (p-cresol-2-ylmethyl) -p-cresol and 1 g (9 mmol) of 2-ethyl-4-methylimidazole (2E4MZ) were dissolved in ethyl acetate and allowed to stand at room temperature. The product was obtained by crystallization, filtration, and drying under reduced pressure by ¹ H-NMR, TG-DSC and XRD, and 2,6-bis (p-cresol-2-ylmethyl). ) -P-cresol and 2-ethyl-4-methylimidazole were confirmed to be a 1: 1 (molar ratio) inclusion compound (inclusion compound A), and the measurement results are shown in FIGS.
The measurement conditions for each spectrum are as follows.
[XRD]
Device: Ultimate IV (manufactured by Rigaku Corporation)
X-ray source: Cu 40 kV / 40 mA
Measurement method: Concentration method Filter: Kβ filter Scan speed: 5 ° / min.
[TG-DSC]
Apparatus: TGA-DSC1 (manufactured by METTLER TOLEDO)
AL PAN seal measurement temperature range: room temperature to 500 ° C
Temperature increase rate: 20 ° C./min.
N ₂ flow rate: 50 mL / min
Sample amount: 3mg
The endothermic peak tops of 2,6-bis (p-cresol-2-ylmethyl] -p-cresol and 2-ethyl-4-methylimidazole are 215 ° C., 57 ° C. and 202 ° C., respectively. The compound had a temperature of 142 ° C. The weight-decreasing onset temperatures of 2,6-bis (p-cresol-2-ylmethyl] -p-cresol and 2-ethyl-4-methylimidazole were 176 ° C. and 100 ° C., respectively. The clathrate was 128 ° C. while it was at ° C.

(Synthesis Example 2)
2,6-bis (p-cresol-2-ylmethyl) -p-cresol 3.16 g (9 mmol), 2-ethyl-4-methylimidazole 1 g (9 mmol) and ethyl acetate 15 ml were refluxed and stirred for 3 hours, after cooling. The product was obtained by ¹ H-NMR, TG-DSC and XRD, and then 2,6-bis (p-cresol-2-ylmethyl] -p-cresol. And 2-ethyl-4-methylimidazole in a 1: 1 (molar ratio) inclusion compound (inclusion compound A).

(Synthesis Example 3)
2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol 4 g (8.5 mmol) and 2-ethyl-4-methylimidazole 0.94 g (8.5 mmol) in ethyl acetate It was dissolved, allowed to stand at room temperature for crystallization, filtered, and dried under reduced pressure to obtain a product. The obtained product was analyzed by ¹ H-NMR, TG-DSC and XRD with 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol 4 g (8.5 mmol) and 2 -It was confirmed that it was a 1: 1 (molar ratio) inclusion compound (inclusion compound B) of ethyl-4-methylimidazole. The measurement results are shown in FIGS.
The endothermic peak tops of 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol and 2E4MZ are 179 ° C., 57 ° C. and 202 ° C., respectively, while the inclusion compound is 162 ° C. Moreover, while the weight onset decreasing temperatures of 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol and 2E4MZ are 169 ° C. and 100 ° C., respectively, the inclusion compound Was 138 ° C.

(Synthesis Example 4)
2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol 12 g (25.6 mmol), 2.E4MZ 2.82 g (25.6 mmol) and ethyl acetate 30 ml were stirred at reflux for 3 hours, and cooled. Thereafter, the product was obtained by filtration and drying under reduced pressure. The obtained product was analyzed by ¹ H-NMR, TG-DSC and XRD with 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol 4 g (8.5 mmol) and 2E4MZ. It was confirmed that the compound was a 1: 1 (molar ratio) inclusion compound (inclusion compound B).

[Manufacture of epoxy resin]
(Prescription Example 1)
5 g of epoxy resin (trade name: Epototo (registered trademark) YD-128, manufactured by Toho Kasei Co., Ltd.), 0.2 g of inclusion compound A obtained in Synthesis Example 1 in terms of 2-ethyl-4-methylimidazole was added. did. Epoxy resin composition A was obtained by kneading at 25 ° C. for 10 minutes.

(Prescription example 2)
5 g of epoxy resin (trade name: Epototo YD-128, manufactured by Toho Kasei Co., Ltd.) and 0.2 g of inclusion compound B in terms of 2-ethyl-4-methylimidazole were added. Epoxy resin composition B was obtained by kneading at 25 ° C. for 10 minutes.

(Comparative formulation example 1)
Instead of inclusion compound A, an inclusion compound comprising a composition ratio of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2-ethyl-4-methylimidazole of 1: 2 (molar ratio) Except that was used, an epoxy resin composition C was obtained in the same manner as in Formulation Example 1.

(Comparative formulation example 2)
Epoxy resin composition D was obtained in the same manner as in Formulation Example 1 except that 2-ethyl-4-methylimidazole was used instead of inclusion compound A.

(DSC measurement 1 of epoxy resin compositions A to D)
A portion of each of the epoxy resin compositions A to D obtained in Formulation Examples 1 and 2 and Comparative Formulation Examples 1 and 2 was sampled, and the exotherm based on the curing reaction of the epoxy resin composition was measured with a differential scanning calorimeter. .

The respective DSC charts of the epoxy resin compositions A to D are shown in FIGS. In the figure, the horizontal axis represents the measured temperature (° C.), and the vertical axis represents the calorific value (Heat Flow / mW).
The measurement conditions are as follows.
Apparatus: DSC Q2000 (manufactured by TA Instruments Japan)
AL pan seal measurement temperature range: room temperature to 250 ° C
Temperature rising rate 10 ° C./min.
N ₂ flow rate: 50 mL / min
Sample amount: 3mg

(DSC measurement 2 of epoxy resin compositions A to D)
The obtained epoxy resin compositions A to D were fixed at a temperature of 80 ° C., the time axis was taken on the horizontal axis, and DSC was measured. The results are shown in FIGS.

(Reference example)
In Patent Document 10 (Japanese Patent Laid-Open No. 56-59841), a phenolic compound having at least 3 phenolic hydroxyl groups per molecule and a tetra-substituted borate compound of various imidazoles are melted at a temperature of 80 to 180 ° C. A mixed curing agent is described, and it was verified whether the curing agent was an inclusion compound.
According to the examples of the present application, 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol and 2E4MZ were mixed at a molar ratio of 1: 1 and heated at 180 ° C. for 30 minutes. Melt mixed. TG-DSC of the obtained mixture was measured. The result is shown in FIG.
Since no endothermic peak was observed, it was found that the above mixture did not contain an inclusion compound.

Claims (3)

Formula (I)

(In the formula, R is a hydroxy group, a nitro group, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a hydroxy group, a C6-C10 aryl group, a C6-C10 aryl C1-C10 alkyl group, A C1-C10 acyl group, a C1-C10 alkoxycarbonyl group, a carboxyl group, a cyano group, or a carbamoyl group, m represents an integer of 0 or 1-3, and a represents 1 or 2.) An inclusion compound containing a compound represented by the formula: 2-ethyl-4-methylimidazole. An epoxy resin composition containing the following components (A) and (B).
(A) Epoxy resin (B) Formula (I)

(In the formula, R is a hydroxy group, a nitro group, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a hydroxy group, a C6-C10 aryl group, a C6-C10 aryl C1-C10 alkyl group, A C1-C10 acyl group, a C1-C10 alkoxycarbonyl group, a carboxyl group, a cyano group, or a carbamoyl group, m represents an integer of 0 or 1-3, and a represents 1 or 2.) An inclusion compound containing 2-ethyl-4-methylimidazole and A cured product obtained by curing the epoxy resin composition according to claim 2.