JP2000355623A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cationic polymerization catalyst composition which can accelerate the curing rate of a cationically polymerizable compound and can improve the final conversion by mixing an α,β-diol compound having a specified structure with a cationic polymerization initiator. SOLUTION: A curable composition is provided which is prepared by mixing 100 pts.wt. cationically polymerizable compound with a cationic polymerization catalyst composition comprising 0.1-50 pts.wt. α,β-diol compound represented by formula I, such as a 1,2-cyclohexanediol derivative and 0.01-20 pts.wt. cationic polymerization initiator such as a sulfonium salt represented by formula II or an iodonium salt represented by formula III. The cationically polymerizable compound used is exemplified by an oxirane compound being an epoxy compound such as cyclohexene oxide or an oxetane compound such as 3,3- dimethyloxetane. In the formulae, R1 and R2 are each an alkyl or phenyl; R3 is a 1-8C alkyl or phenyl; R4 is phenyl, naphthyl, or the like; Ar, Ar1, and Ar2 are each phenyl or naphthyl; and X and Y are each a non-nucleophilic anionic residue.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cationic polymerization catalyst composition and a curable resin composition containing the same, such as an epoxy curable composition having improved curability. The curable resin composition of the present invention can be cured in a short time by heating or light, and since the cured product has excellent properties, a molding resin, a casting resin, a paint, an adhesive, a sealant, It is suitably used as a stopping agent, ink and the like.

[0002]

BACKGROUND OF THE INVENTION As thermal cationic polymerization initiators, onium salts such as sulfonium salts, ammonium salts, and phosphonium salts, and silanol-aluminum complexes are known. For example, JP-A-1-96169 and JP-A-2-96.
1470, JP-A-2-255646, JP-A-2-268173, JP-A-3-11044, JP-A-3-115262, JP-A-4-117
7, JP-A-4-327574, JP-A-4-327574
308563, JP-A-4-328106,
JP-A-5-132461, JP-A-5-13246
No. 2, JP-A-5-140132, JP-A-5-140132
No. 140209, JP-A-5-140210,
JP-A-5-170737 and JP-A-5-23019
0, JP-A-5-230189, JP-A-6-230189
No. 271532, JP-A-6-271544,
JP-A-6-321897, JP-A-6-32119
No. 5, JP-A-6-345726, JP-A-6-345726
345733, JP-A-6-814754,
It is described in JP-A-7-25852, JP-A-7-25863, JP-A-7-89909, and the like.

Onium salts such as sulfonium salts, iodonium salts, ammonium salts and phosphonium salts are known as cationic photopolymerization initiators.
JP-A-15-151997, JP-A-50-158680, JP-A-50-151996, JP-A-2-17
No. 8303, and the like, which describes that it can be used as a catalyst for curing a cationically polymerizable compound such as an epoxy compound by radiation such as light, an electron beam, or X-ray.

A curing system using a cationic polymerization catalyst can cure in a short period of time, so that it has high productivity, is suitable for energy saving and resource saving, and is excellent in environmental aspects due to reduced carbon dioxide emission. I have. In addition, since an epoxy compound can be used as a curing monomer, it is said that the cured product has excellent physical properties.

[0005] Alcohols, particularly caprolactone polyols, are known to be effective as compounds that accelerate the cationic curing reaction of epoxy compounds. Also,
As alcohols for improving the curing rate, it is said that primary alcohols are effective and secondary alcohols are not effective.

[0006]

However, many alcohols other than caprolactone polyols have a small ability to improve the curing speed and, in some cases, have no effect. On the other hand, caprolactone polyols are effective in increasing the curing rate, but have limitations, for example, there is a wall in the final reaction rate. It is also known that in some cases, the properties of the cured product such as a decrease in glass transition temperature and a decrease in solvent resistance may be caused.

[0007] Compounds that do not accelerate the cationic curing reaction of epoxy compounds more than caprolactone polyols or reduce the properties of cured products are not known at present, and therefore epoxy compounds having good curability and properties of cured products are required. Obtaining it was considered difficult at present. The present invention has been made in view of these circumstances, and an object thereof is to increase the curing rate of a cationic polymerizable compound such as an epoxy compound to a caprolactone polyol or more, and to improve a final polymerization rate in a cationic polymerization catalyst composition. And a curable resin composition containing the same.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have found that they comprise a cationic polymerization initiator and a specific α, β diol compound and a cationically polymerizable compound such as an epoxy compound. By using a curable resin composition, the curing rate of a cationically polymerizable compound such as an epoxy compound is accelerated more than when caprolactone polyols are used, and it is found that the final reaction rate is improved, and the present invention is completed. Reached.

That is, the present invention relates to a cationic polymerization initiator comprising a compound represented by the general formula (I):

Embedded image (Wherein, R ₁ and R ₂ are each independently, represent an alkyl group which may be substituted, also R ₁ and R ₂ represent a bond to the group which may form a ring structure. Α),
a cationic polymerization catalyst composition containing a β-diol compound (claim 1); and the α, β-diol compound represented by the general formula (I) is a 1,2-cyclohexanediol derivative. The present invention relates to a cationic polymerization catalyst composition according to claim 1 (claim 2).

In the present invention, the cationic polymerization initiator preferably has the general formula (II)

Embedded image (In the formula, Ar represents an optionally substituted phenyl group or an optionally substituted naphthyl group, and R ₃ represents
A C8 alkyl group or a phenyl group which may be substituted, and R ₄ represents a phenyl group which may be substituted, a naphthyl group which may be substituted, an alkyl group which may be substituted, a cycloalkyl group, X represents an alkenyl group or an indanyl group, and X represents a non-nucleophilic anionic residue. ) Or a general formula (III)

Embedded image (Wherein, Ar ₁ and Ar ₂ each independently represent a phenyl group which may be substituted or a naphthyl group which may be substituted, and Y represents a non-nucleophilic anion residue). The cationic polymerization catalyst composition according to claim 1 or claim 2, which is an iodonium salt compound represented by the following formula (3).

The present invention further provides a curable resin composition comprising the cationic polymerization catalyst composition according to any one of claims 1 to 3 and a cationic polymerizable compound (claim 4). 5. The curable resin composition according to claim 4, wherein the curable resin compound is an oxirane compound, and the oxirane compound is an epoxy compound or an oxetane compound.
The curable resin composition (Claim 7) according to claim 6, wherein the epoxy compound is an alicyclic epoxy compound. The curable resin composition according to any one of claims 4 to 7, wherein the composition further contains a radical polymerizable compound (claim 8).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the α, β diol compound represented by the general formula (I) used in the present invention, R ₁ and R ₂ each independently represent an optionally substituted alkyl group. In particular,
Methyl group, ethyl group, isopropyl group, n-butyl group,
An s-butyl group and the like can be exemplified. Further, as a substituent of these alkyl groups, a methylmethoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group,
An alkoxy group such as a decyloxy group and a dodecyloxy group,
Acetoxy group, propionyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group, methoxycarbonyl group, ethoxycarbonyl group, carbonyl group such as benzoyloxy group, phenyl group, halogen atom such as fluorine, chlorine, bromine, iodine, cyano group , A nitro group, a hydroxy group and the like, and the substitution position is not particularly limited. R ₁ and R ₂ may combine to form a ring structure such as a cyclohexane ring.

Specific examples of the α, β diol compound represented by the general formula (I) are as follows.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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As the cationic polymerization initiator used in the present invention, onium salts such as sulfonium salts, ammonium salts, phosphonium salts and the like can be used, and among them, sulfonium salts and iodonium salts are preferably used. ) Or a sulfonium salt or an iodonium salt represented by the general formula (III).

[0022]

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[0023]

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In the general formula (II), Ar represents an optionally substituted phenyl group or an optionally substituted naphthyl group. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an alkyl group such as a hexyl group, a methoxy group, an ethoxy group, a propoxy group, Alkoxy groups such as butoxy group, hexyloxy group, decyloxy group and dodecyloxy group, acetoxy group, propionyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group, methoxycarbonyl group, carbonyl group such as ethoxycarbonyl group and benzoyloxy group Phenylthio group, halogen atoms such as fluorine, chlorine, bromine and iodine, cyano group, nitro group, hydroxy group and the like. Further, the substitution position is not particularly limited.

R ₃ represents a C1-C8 alkyl group or an optionally substituted phenyl group. Specifically, C1
Examples of the C8 to C8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group. Further, as a substituent of the optionally substituted phenyl group,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, decyloxy Groups, alkoxy groups such as dodecyloxy group, acetoxy group, propionyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group, methoxycarbonyl group, ethoxycarbonyl group, carbonyl group such as benzoyloxy group, phenylthio group, fluorine, chlorine, Examples thereof include a halogen atom such as bromine and iodine, a cyano group, a nitro group and a hydroxy group, and the substitution position is not particularly limited.

R ₄ represents an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group,
Or an indanyl group. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, alkyl group such as hexyl group, methoxy group, ethoxy group, propoxy group,
Alkoxy groups such as butoxy group, hexyloxy group, decyloxy group and dodecyloxy group, acetoxy group, propionyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group, methoxycarbonyl group, carbonyl group such as ethoxycarbonyl group and benzoyloxy group ,
Phenylthio group, halogen atom such as fluorine, chlorine, bromine, iodine, etc., phenyl group or naphthyl group, methoxy group, ethoxy group which may be substituted without particular limitation on the substitution position with cyano group, nitro group, hydroxy group, etc. , Propyl group, butoxy group, hexyloxy group, decyloxy group, alkoxy group such as dodecyloxy group, acetoxy group, propionyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group, methoxycarbonyl group, ethoxycarbonyl group, benzoyloxy group Such as carbonyl group, phenylthio group, halogen atom such as fluorine, chlorine, bromine and iodine, cyano group, nitro group, hydroxy group or alkyl group which may be substituted without particular limitation on the substitution position. , Cyclohexyl group, cyclohexanoni Group, a cyclopentyl group, 1-acenaphthenyl group, bicyclononyl group, a norbornyl group,
Examples include a bicycloalkyl group such as a coumarinyl group, a dihydrobenzofuranyl group, and a camphor group, an alkenyl group, a 1-indanyl group, and a 2-indanyl group.

X represents a non-nucleophilic anion residue, and specific examples thereof include B (C ₆ F ₅ ) ₄ , SbF ₆ , AsF ₆ , PF _{6 and} BF ₄ .

In the formula (III), Ar ₁ and Ar ₂ are
Each independently represents a phenyl group which may be substituted or a naphthyl group which may be substituted. Specific examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group and a hexyl group, a methoxy group, an ethoxy group, and a propoxy group. , Butoxy group, hexyloxy group, decyloxy group, alkoxy group such as dodecyloxy group, acetoxy group, propionyloxy group, decylcarbonyloxy group, dodecylcarbonyloxy group,
Methoxycarbonyl group, ethoxycarbonyl group, carbonyl group such as benzoyloxy group, phenylthio group, fluorine, chlorine, bromine, halogen atom such as iodine, cyano group,
Examples thereof include a nitro group and a hydroxy group. Further, the substitution position is not particularly limited.

Y represents a non-nucleophilic anionic residue, and specific examples thereof include B (C ₆ F ₅ ) ₄ , SbF ₆ , AsF ₆ , PF _{6 and} BF ₄ .

The cationically polymerizable compound used in the present invention can be used without any limitation as long as it is a generally known monomer, oligomer or polymer having a cationically polymerizable group. However, an oxirane compound such as an epoxy compound or an oxetane compound is preferably used.

(A) As the vinyl compound, styrene, α
Styrene compounds such as -methylstyrene, p-methoxystyrene, pt-butoxystyrene, methyl vinyl ether, n-butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-phenoxyethyl vinyl ether, -Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether,
Stearyl vinyl ether, alkyl vinyl ether compounds such as 2-acetoxyethyl vinyl ether, allyl vinyl ether, alkenyl vinyl ether compounds such as 2-methacryloyloxyethyl vinyl ether, 2-acryloyloxyethyl vinyl ether, phenyl vinyl ether, aryl vinyl ether compounds such as p-methoxyphenyl vinyl ether, N-vinyl carbazole, cationically polymerizable nitrogen-containing compounds such as N-vinyl pyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, hydroquinone divinyl ether,
And polyfunctional vinyl compounds such as sasolcinol divinyl ether.

(B) As epoxy compounds, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene mono Oxide, 1,2-dodecylene oxide, epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide Monofunctional monomers such as, 3-vinylcyclohexene oxide,
1,3-tetradecadienedoxide, limonenedoxide, 3,4-epoxycyclohexylmethyl-
(3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) adipate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak And polyfunctional epoxy compounds such as polyepoxy resin and polyglycidyl ether of polyhydric alcohol. Preferably, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, limonenedioxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxycyclohexyl) carboxylate And alicyclic epoxies such as di (3,4-epoxycyclohexyl) adipate.

(C) As bicycloorthoester compounds, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4-
Compounds such as hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane are exemplified.

(D) As a spiro orthocarbonate compound, 1,5,7,11-tetraoxaspiro [5,
5] undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, 1,
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Compounds such as 1,4,6-trioxaspiro [4,5] decane are exemplified.

(E) As the oxetane compound, 3,3-
Dimethyl oxetane, 3,3-bis (chloromethyl) oxetane, 2-hydroxymethyl oxetane, 3-methyl-3-oxetane methanol, 3-methyl-3-methoxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, resorcinol Bis (3-methyl-3
-Oxetanylethyl) ether and m-xylylenebis (3-ethyl-3-oxetanylethyl ether). These can be used alone or
More than one species may be used in combination.

In the present invention, the mixing ratio of the cationic polymerization initiator and the cationically polymerizable compound such as an α, β diol compound and an epoxy compound is 100 parts by weight of the cationically polymerizable compound such as an epoxy compound and 0.1 part by weight of the cationic polymerization initiator. The amount is from 0.01 to 20 parts by weight, preferably from 0.1 to 10 parts by weight, from 0.1 to 50 parts by weight, preferably from 0.5 to 30 parts by weight, of the α, β diol compound. If the amount of the cationic polymerization initiator is small, the curability of the cationically polymerizable compound such as an epoxy compound is reduced. If the amount is excessive, the properties of the cured product are reduced. Further, when the amount of the α, β diol compound is small, the curability of the cationically polymerizable compound such as an epoxy compound decreases, and when the amount is excessive, the characteristics of the cured product deteriorate.

The curable resin composition of the present invention comprising a cationic polymerization initiator, a α, β diol compound, and a cationically polymerizable compound such as an epoxy compound can be heated by using a heat cationic polymerization initiator as the cationic polymerization initiator. Can be cured. The curing temperature depends on the thermal cationic polymerization initiator used, and is usually from room temperature to 200 ° C, preferably from 70 to 160 ° C.

On the other hand, the cationic polymerization initiator of the present invention, α,
A curable resin composition comprising a β-diol compound and a cationically polymerizable compound such as an epoxy compound can be cured by light if a cationic photopolymerization initiator is used as the cationic polymerization initiator. As a light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like is used. Semiconductor laser, argon laser, He
It can be easily cured by laser light such as -Cd laser or ionizing radiation such as α-ray, β-ray, γ-ray, neutron beam, X-ray and accelerating electron beam. Furthermore, when an appropriate sensitizer such as thioxanthones is used in combination, the photocurability can be improved.

For controlling the physical properties, curability and the like of the cured product of the curable resin composition according to the present invention, a radical polymerizable compound can be used. As the radical polymerizable compound used in the present invention, any monomers, oligomers and polymers having radical polymerizability can be used regardless of the kind thereof. As the radical polymerizable monomer, monofunctional or polyfunctional acrylate or methacrylate monomer, etc., as the radical polymerizable oligomer, epoxy acrylate, epoxy methacrylate, polyester acrylate, polyester methacrylate, polyether acrylate, polyether methacrylate, polyurethane acrylate, Polyurethane methacrylate, polybutadiene acrylate, polybutadiene methacrylate, and the like, and radical polymerizable polymers include polyester, polybutadiene, and polyether. , Urethane, each acrylates such as epoxy, the methacrylate compounds, can be exemplified unsaturated polyesters. Examples of the radical polymerizable reactive diluent include acrylic acid ester monomers such as acrylic acid and ethyl acrylate, methacrylic acid ester monomers such as methacrylic acid and methyl methacrylate, and styrene.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited to the examples. Then, in the following examples, as the cationic polymerizable compound, an alicyclic epoxy compound “UVR-6110” manufactured by UCC was used, and as the cationic photopolymerization initiator, a cationic polymerization catalyst “UVI-6990” manufactured by UCC was used.
Was used.

Example 1 100 parts by weight of a cationically polymerizable compound "UVR-6110" was mixed with 4 parts by weight of a photocationic polymerization initiator "UVI-6990" and alcohols described in (Test categories 1 to 3) in Table 1. FT-IR (MAGNA76) manufactured by Nicole
0) using a mercury lamp with an illuminance of 495 mw / cm ² ,
The rate of decrease of the absorption of the epoxy group at 790 cm ^-1 was measured in real time. U calculated based on the measurement result
The reaction rate after 30 seconds of V irradiation is shown in Table 1. In addition, instead of the alcohols described in (Test categories 1 to 3) in Table 1, Table 1
Comparative Examples were performed in the same manner as in Examples except that the alcohols described in (Test categories 4 to 6) were used, and those not blended with alcohols were used as controls.

[0042]

[Table 1]

As shown in Table 1, when the α, β diol of the present invention was used (test categories 1 to 3), the conventional alcohols were used (test categories 4 to 6) or alcohols were used. The response was found to be accelerated as compared to the control without.

[0044]

The cationic polymerization catalyst composition of the present invention is capable of accelerating the curing rate of a cationically polymerizable compound such as an epoxy compound by heating or light to a level higher than that of caprolactone polyols, and curing the composition in a short time. Since the final reaction rate can be improved, and the cured product of the curable resin composition of the present invention has excellent properties, molding resins, casting resins, paints, and adhesives which have been considered difficult to adapt so far. It is suitably used for agents, sealants and inks.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Takahashi 12-54, Goi-Minamikaigan, Ichihara-shi, Chiba Prefecture Nippon Soda Co., Ltd. Nippon Soda Co., Ltd. Functional Products Laboratory F-term (reference) 4J005 AA04 AA07 BB02 4J036 AA01 AB07 AC08 AD08 AF06 AF07 DA04 DB05 DB09 DB10 GA01 GA03 HA02 JA01 JA06 JA07

Claims (8)

[Claims] 1. A cationic polymerization initiator comprising a compound represented by the general formula (I): (Wherein, R ₁ and R ₂ are each independently, represent an alkyl group which may be substituted, also R ₁ and R ₂ represent a bond to the group which may form a ring structure. Α),
A cationic polymerization catalyst composition comprising a β-diol compound. 2. The cationic polymerization catalyst composition according to claim 1, wherein the α, β diol compound represented by the general formula (I) is a 1,2-cyclohexanediol derivative. 3. The cationic polymerization initiator represented by the general formula (II): (In the formula, Ar represents an optionally substituted phenyl group or an optionally substituted naphthyl group, and R ₃ represents
A C8 alkyl group or a phenyl group which may be substituted, and R ₄ represents a phenyl group which may be substituted, a naphthyl group which may be substituted, an alkyl group which may be substituted, a cycloalkyl group, X represents an alkenyl group or an indanyl group, and X represents a non-nucleophilic anionic residue. Or a sulfonium salt compound represented by the general formula (III): (Wherein, Ar ₁ and Ar ₂ each independently represent a phenyl group which may be substituted or a naphthyl group which may be substituted, and Y represents a non-nucleophilic anion residue). 3. The cationic polymerization catalyst composition according to claim 1, which is an iodonium salt compound represented by the formula: 4. A curable resin composition comprising the cationic polymerization catalyst composition according to claim 1 and a cationically polymerizable compound. 5. The curable resin composition according to claim 4, wherein the cationically polymerizable compound is an oxirane compound. 6. The curable resin composition according to claim 5, wherein the oxirane compound is an epoxy compound or an oxetane compound. 7. The curable resin composition according to claim 6, wherein the epoxy compound is an alicyclic epoxy compound. 8. The curable resin composition according to claim 4, wherein the curable resin composition further contains a radical polymerizable compound.