JP7103852B2 - Curable composition and its cured product - Google Patents

Description

The present invention relates to a curable composition using an inclusion compound having a binaphthol compound as a host as a curing agent and / or a curing accelerator for an epoxy resin, a method for producing the same, and a cured product of the curable composition.

It is known that the clathrate compound can enhance the chemical stability of the guest compound and can improve the handleability by making the guest compound non-volatile or powdered. Further, clathrate compounds are used in the field of separation materials utilizing selective separability by clathrate.

For example, the 1,1'-bi-2-naphthol compound is known to function as a host compound capable of containing small molecules, and is published in International Publication No. 2008/053496 (Patent Document 1) and International Publication No. 1. 2010/079504 (Patent Document 2) proposes a method for dividing an optically active substance by forming a diastereomeric salt by inclusionlizing a racemic compound in 1,1'-bi-2-naphthol. ing.

On the other hand, the clathrate compound can also be used as a temperature-sensitive material utilizing the fact that the release of the guest compound depends on the temperature. For example, Japanese Patent Application Laid-Open No. 11-71449 (Patent Document 3) uses a predetermined alkanetetrakisphenol such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host compound, and imidazoles and the like as guests. It has been proposed to use a clathrate compound as a compound as a curing agent or a curing accelerator for an epoxy resin.

However, these documents do not describe the use of a clathrate compound having a 1,1'-bi-2-naphthol compound as a host compound as a curing agent for a resin or the like.

International Publication No. 2008/053496 International Publication No. 2010/07954 Japanese Unexamined Patent Publication No. 11-71449

Therefore, an object of the present invention is a novel curable composition containing a clathrate compound having a 1,1'-bi-2-naphthol compound as a host compound as a curing agent and / or a curing accelerator for a resin, and a novel curable composition thereof. The method and the present invention are to provide a cured product of the curable composition.

Another object of the present invention is to provide a curable composition having high storage stability and which can be rapidly cured by heating, a method for producing the same, and a cured product of the curable composition.

Still another object of the present invention is to obtain a curable composition and a method for producing the same, and a cured product of the curable composition, which can reduce the amount of the clathrate compound used as a curing agent and / or a curing accelerator. To provide.

As a result of diligent studies to achieve the above problems, the present inventors have found that an inclusion compound having a 1,1'-bi-2-naphthol compound as a host compound is effective as a curing agent and / or a curing accelerator for a resin. The present invention was completed by finding that it can be used for.

That is, the curable composition of the present invention contains an epoxy resin and an inclusion compound as a curing agent and / or a curing accelerator, and the inclusion compound is a host compound represented by the following formula (1). , A 5- or 6-membered heterocycle containing a plurality of nitrogen atoms or a guest compound having a fused heterocycle thereof is included as a constituent atom of the ring.

(In the formula, R ¹ and R ² are independent substituents, m is an independent integer of 0 to 4, and n is an independent integer of 0 to 2).

In the above formula (1), R ¹ and R ² are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, an alkoxycarbonyl group and a halogen. It may be an atom, a nitro group, a cyano group or a substituted amino group, m may be an integer of 0 to 2, and n may be 0 or 1.

The guest compound may contain a compound represented by the following formula (2).

(In the formula, R ³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyanoalkyl group, or a triazine-alkyl group; R ⁴ to R ⁶ are a hydrogen atom, a halogen atom, and a nitro. It represents a group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and the alkyl group may have a hydroxyl group; R ³ and R ⁴ are bonded to each other and adjacent nitrogen atoms and adjacent nitrogen atoms and A ring may be formed with a carbon atom; p indicates an integer of 0 to 3; a double line of a solid line and a broken line indicates a single bond or a double bond).

The guest compound may contain a compound represented by the following formulas (2a) and / or (2b).

(In the equation, q indicates an integer of 0 to 5; R ³ to R ⁶ and the double line of the solid line and the broken line are the same as in the above equation (2)).

The guest compound may contain at least one imidazole compound selected from 2-alkylimidazole, 2-arylimidazole, 2,4-dialkylimidazole and 1-cyanoethyl-2,4-dialkylimidazole. The clathrate compound may contain 0.5 to 5 mol of the guest compound with respect to 1 mol of the host compound. The epoxy resin may be a liquid epoxy resin. The curable composition may contain the clathrate compound in a ratio of 0.1 to 25 parts by mass with respect to 100 parts by mass of the epoxy resin.

The present invention comprises a clathrate compound containing a host compound represented by the above formula (1) and a 5- or 6-membered heterocycle containing a plurality of nitrogen atoms as a constituent atom of the ring or a guest compound having a fused heterocycle thereof. , Includes a method of producing the curable composition by mixing with an epoxy resin. The present invention also includes a cured product obtained by curing the curable composition.

In addition, in this specification and claims, the number of carbon atoms of a substituent may be indicated by C ₁ , C ₆ , C ₁₀ , and the like. For example, an alkyl group having 1 carbon atom is indicated by "C ₁ alkyl", and an aryl group having 6 to 10 carbon atoms is indicated by "C _6-10 aryl".

INDUSTRIAL APPLICABILITY The present invention can provide a novel curable composition containing a clathrate compound having a 1,1'-bi-2-naphthol compound as a host compound as a curing agent and / or a curing accelerator for a resin. Further, since the curable composition contains the clathrate compound, it has high storage stability and can be rapidly cured by heating. Further, in the present invention, since the molecular weight of the host compound is not so large and the clathrate of the guest compound to 1 mol of the host compound is large, the clathrate compound which tends to be used in a large amount is usually used as a curing agent and / or a curing accelerator. Despite being used as, the amount used can be reduced.

FIG. 1 is a ¹ H-NMR spectrum of BINOL. FIG. 2 is a ¹ H-NMR spectrum of 2E4MZ. FIG. 3 is a ¹ H-NMR spectrum of 2 MZ-H. FIG. 4 is a ¹ H-NMR spectrum of 2E4MZ-CN. FIG. 5 is a ¹ H-NMR spectrum of 2PZ-PW. FIG. 6 is a ¹ H-NMR spectrum of the clathrate compound of Example 1. FIG. 7 is a ¹ H-NMR spectrum of the clathrate compound of Example 2. FIG. 8 is a ¹ H-NMR spectrum of the clathrate compound of Example 3. FIG. 9 is a ¹ H-NMR spectrum of the clathrate compound of Example 4. FIG. 10 is a BINOL XRD chart. FIG. 11 is an XRD chart of the clathrate compound of Example 1. FIG. 12 is an XRD chart of the clathrate compound of Example 2. FIG. 13 is an XRD chart of the clathrate compound of Example 3. FIG. 14 is an XRD chart of the clathrate compound of Example 4. FIG. 15 is a TGA chart of BINOL. FIG. 16 is a 2E4MZ TGA chart. FIG. 17 is a 2MZ-H TGA chart. FIG. 18 is a TGA chart of 2E4MZ-CN. FIG. 19 is a TGA chart of 2PZ-PW. FIG. 20 is a TGA chart of the clathrate compound of Example 1. FIG. 21 is a TGA chart of the clathrate compound of Example 2. FIG. 22 is a TGA chart of the clathrate compound of Example 3. FIG. 23 is a TGA chart of the clathrate compound of Example 4.

The curable composition of the present invention contains an epoxy resin, a curing agent and / or a curing accelerator, and contains a predetermined inclusion compound as the curing agent and / or the curing accelerator.

[Clathrate compound]
In the clathrate compound, a small molecule is incorporated as a guest compound (guest or guest molecule) in the space formed by the host compound (host or host molecule), and the guest is stably present regardless of the covalent bond.

(Host compound)
In the present invention, as the host compound, a 1,1'-bi-2-naphthol compound represented by the following formula (1) can be used.

(In the formula, R ¹ and R ² are independent substituents, m is an independent integer of 0 to 4, and n is an independent integer of 0 to 2).

In the above formula (1), the types of the substituents R ¹ and R ² are not particularly limited as long as the inclusion of the guest compound is not impaired, and the halogen atom, nitro group, cyano group, hydrocarbon group, group-OR ¹⁰ and the like are not particularly limited. Group-SR ¹⁰ , Group-COOR ¹⁰ , Group-COR ¹⁰ , Group-CON (R ¹⁰ ) ₂ (In each formula, R ¹⁰ is an independent hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl. Indicates a group, etc.)
You can choose from a wide range such as. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like.

Typical examples of R ¹ and R ² include hydrocarbon groups such as alkyl group, cycloalkyl group, aryl group and aralkyl group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group and cyclo. Examples thereof include an alkylthio group, an arylthio group, an aralkylthio group, an acyl group, a carboxyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group and a substituted amino group.

Examples of the alkyl group include a linear or branched C _1-10 alkyl such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. Examples thereof include a linear or branched C _1-6 alkyl group, and more preferably a linear or branched C _1-4 alkyl group.

Examples of the cycloalkyl group include a C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, preferably a C _5-8 cycloalkyl group, and more preferably a C _5-6 cycloalkyl group.

Examples of the aryl group include a C _6-12 aryl group such as a phenyl group, a biphenyl group and a naphthyl group.

Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group.

The hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group may have a substituent such as an alkyl group or a halogen atom, and may form, for example, an alkylphenyl group. good. Examples of the alkylphenyl group include a methylphenyl group (tolyl group) and a dimethylphenyl group (xylyl group).

Examples of the alkoxy group include a linear or branched C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group and a t-butoxy group, preferably C _1-8 . Alkoxy groups, more preferably C _1-6 alkoxy groups and the like can be mentioned.

Examples of the cycloalkoxy group include a C _5-10 cycloalkoxy group such as a cyclohexyloxy group.

Examples of the aryloxy group include a _C6-10 aryloxy group such as a phenoxy group.

Examples of the aralkyloxy group include a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group.

Examples of the alkylthio group include a C _1-10 alkylthio group corresponding to the alkoxy group such as a methylthio group. Examples of the cycloalkylthio group include a C _5-10 cycloalkylthio group such as a cyclohexylthio group. Examples of the arylthio group include a _C6-10 arylthio group such as a thiophenoxy group. Examples of the aralkylthio group include a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group.

Examples of the acyl group include a C _1-6 acyl group such as an acetyl group. Examples of the alkoxycarbonyl group include a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Examples of the substituted amino group include a dialkylamino group and a bis (alkylcarbonyl) amino group. Examples of the dialkylamino group include a diC _1-4 alkylamino group such as a dimethylamino group. Examples of the bis (alkylcarbonyl) amino group include a bis (C _1-4 alkyl-carbonyl) amino group such as a diacetylamino group.

When the substituents R ¹ and R ² are provided, the preferred substituents R ¹ and R ² are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group and an acyl group. Examples include groups, alkoxycarbonyl groups, halogen atoms, nitro groups, cyano groups or substituted amino groups; more preferably alkoxy groups such as alkyl groups, aryl groups or linear or branched C _1-6 alkoxy groups. ; More preferably, it is an alkyl group or an aryl group. Particularly preferably, it is a linear or branched C _1-6 alkyl group or C _6-12 aryl group, and among them, a linear or branched C _1-4 alkyl group such as a methyl group, or phenyl. It is a C _6-10 aryl group such as a group.

The substitution number m of the substituent ^R1 may be, for example, an integer of about 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly 0. The two substitution numbers m in two different naphthalene rings may be different from each other, but are usually the same. The types of ^R1 that replace two different naphthalene rings may be the same or different from each other. When m is 2 or more, the types of ² or more R1s substituted with the same naphthalene ring may be the same or different from each other.

The number of substitutions n of the substituent ^R2 is, for example, 0 or 1, preferably 0. The two substitution numbers n in two different naphthalene rings may be different from each other, but are usually the same. The types of R ² that replace two different naphthalene rings may be the same or different from each other. Further, when n is 2, the types of two R ^2s substituted with the same naphthalene ring may be the same or different from each other.

Typical examples of the compound represented by the formula (1) include 1,1'-bi-2-naphthol (BINOL) and the like.

(Guest compound)
The clathrate compound contains, as a guest compound, a predetermined heterocyclic compound, that is, a compound having a 5- or 6-membered heterocycle containing a plurality of nitrogen atoms as a constituent atom of the ring or a condensed heterocycle thereof. The nitrogen atom may be, for example, a basic nitrogen atom, and the number of the nitrogen atoms is, for example, 2 to 5, preferably 2 to 4, more preferably 2 to 3, and particularly 2 pieces. Is. The 5- or 6-membered heterocycle may be either an aliphatic heterocycle (or a non-aromatic heterocycle) or an aromatic heterocycle. Further, the 5- or 6-membered heterocycle may be condensed with any ring of an aliphatic or aromatic hydrocarbon ring or another heterocycle to form the condensed heterocycle.

Examples of such a heterocyclic compound (or guest compound) include monocyclic heterocyclic compounds such as piperazines and triazines, triethylenediamine (DABCO; 1,4-diazabicyclo [2.2.2] octane) and the like. Examples thereof include condensed polycyclic heterocyclic compounds. Examples of piperazines include piperazine; N, N'-dialkylpiperazine such as N, N'-dimethylpiperazine; N-aminoalkylpiperazine such as N- (aminoethyl) piperazine; 1- (2-dimethylaminoethyl). Examples thereof include N-dialkylaminoethyl-N'-alkylpiperazine such as -4-methylpiperazine. Examples of triazines include triazine, N, N', N "-tris (dimethylaminopropyl) hexahydro-s-triazine and the like.

The heterocyclic compound (or guest compound) may contain the above compound, but preferably contains the compound represented by the following formula (2).

(In the formula, R ³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyanoalkyl group, or a triazine-alkyl group; R ⁴ to R ⁶ are a hydrogen atom, a halogen atom, and a nitro. It represents a group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and the alkyl group may have a hydroxyl group; R ³ and R ⁴ are bonded to each other and adjacent nitrogen atoms and adjacent nitrogen atoms and A ring may be formed with a carbon atom; p indicates an integer of 0 to 3; a double line of a solid line and a broken line indicates a single bond or a double bond).

In the above formula (2), examples of the alkyl group represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group and a t-butyl. Examples thereof include a linear or branched C _1-10 alkyl group such as a group, an n-pentyl group, an n-hexyl group, a nonyl group, an isononyl group, and a decyl group. Preferred alkyl groups are linear or branched C _1-6 alkyl groups.

Examples of the cycloalkyl group represented by R ³ include C _5-10 cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Preferred cycloalkyl groups are C _5-8 cycloalkyl groups, especially C _5-6 cycloalkyl groups and the like.

The aryl group represented by R ³ may be a monocyclic or polycyclic aryl group, and the polycyclic aryl group may be a partially saturated group as well as a completely unsaturated group. Examples of the aryl group include C _6-16 aryl groups such as a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group and a tetralinyl group. Preferred aryl groups are C _6-10 aryl groups such as phenyl groups and naphthyl groups.

The aralkyl group (arylalkyl group) represented by R ³ is a group in which the above aryl group and alkyl group are bonded, and is, for example, a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, or 1-phenyl. -N-hexyl group, naphthalene-1-yl-methyl group, naphthalene-2-yl-ethyl group, 1- (naphthalen-2-yl) -n-propyl group, inden-1-yl-methyl group, etc. Examples thereof include C _6-12 aryl C _1-6 alkyl groups. Preferred aralkyl groups are C _6-10 aryl C _1-4 alkyl groups such as benzyl group and phenethyl group.

The alkyl group, cycloalkyl group, aryl group and aralkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an acyl group, a carboxyl group, an alkoxycarbonyl group, and an alkyl group.

Examples of the halogen atom include a fluorine atom and a chlorine atom. Examples of the alkoxy group include C _1-6 alkoxy groups such as a methoxy group and an ethoxy group. Examples of the acyl group include a formyl group; a C _1-10 alkyl-carbonyl group such as an acetyl group and a propionyl group. Examples of the alkoxycarbonyl group include a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group. Examples of the alkyl group include a C _1-6 alkyl group such as a methyl group and an ethyl group.

Examples of the cyanoalkyl group represented by R ³ include a cyano C _1-6 alkyl group such as a cyanomethyl group and a cyanoethyl group. The preferred cyanoalkyl group is a cyanoC _1-4 alkyl group, more preferably a cyanoC _1-2 alkyl group, and particularly a cyanoethyl group.

In the triazine-alkyl group represented by R ³ , the triazine may be 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, or the like, and is a carbon atom of the triazine ring. May be substituted with an amino group, a hydroxyl group, or the like. Typical triazine-alkyl groups include, for example, 4,6-diamino-1,3,5-triazine-2-yl-methyl group and 4-amino-6-hydroxy-1,3,5-triazine-2. Examples thereof include 1,3,5-triazine-2-yl-C _1-4 alkyl groups such as -yl-methyl group and 4,6-dihydroxy-1,3,5-triazine-2-yl-methyl group. .. A preferred triazine-alkyl group is a 4,6-diamino-1,3,5-triazine-2-yl-C _1-2 alkyl group.

When R ³ and R ⁴ do not form a ring, preferred R ^3s are hydrogen atom, C _1-4 alkyl group, C _6-10 aryl group, C _6-10 aryl C _1-4 alkyl group, cyano C. It is a _1-3 alkyl group, a 1,3,5-triazine-2-yl-C _1-2 alkyl group, or the like, and is usually a hydrogen atom, a cyanoethyl group, or the like.

The halogen atoms represented by R ⁴ to R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl groups represented by R ⁴ to R ⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and n-pentyl group. , N-hexyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, hexadecyl group (palmityl group), heptadecyl group, octadecyl group (stearyl group), etc. Examples thereof include a linear or branched C _1-20 alkyl group. Preferred alkyl groups include, stepwise, linear or branched C _1-18 alkyl groups, linear or branched C _1-12 alkyl groups, linear or branched C _1- . ₁₀ Alkyl group, linear or branched C _1-6 alkyl group, linear or branched C _1-4 alkyl group.

Further, the alkyl group represented by R ⁴ to R ⁶ , in particular, the alkyl group represented by R ⁵ or R ⁶ may have a hydroxyl group. Examples of the alkyl group having a hydroxyl group include a hydroxy C _1-20 alkyl group such as a hydroxymethyl group and a hydroxyethyl group. Preferred hydroxyalkyl groups include, stepwise, hydroxy C _1-18 alkyl group, hydroxy C _1-16 alkyl group, hydroxy C _1-12 alkyl group, hydroxy C _1-8 alkyl group, and hydroxy C _1-6 . It is an alkyl group, a hydroxy C _1-4 alkyl group, more preferably a hydroxy C _1-2 alkyl group, and most preferably a hydroxymethyl group.

Examples of the cycloalkyl group, aryl group, and aralkyl group represented by ^R4 to R6 include the ^same group as the substituent R3 ^, including a preferred embodiment.

The acyl group represented by R ⁴ to R ⁶ may be a hydrogen atom; or a group in which an organic group such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group and a carbonyl group are bonded. .. Examples of the acyl group include a formyl group, a linear or branched alkyl-carbonyl group, an alkenyl-carbonyl group which may have a substituent, an alkynyl-carbonyl group, an aryl-carbonyl group, and a heteroaryl-carbonyl. A group and the like can be exemplified.

Examples of the linear or branched alkyl-carbonyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyyl group, and 3-methylnonanoyl. Group, 8-methylnonanoyl group, 3-ethyloctanoyl group, 3,7-dimethyloctanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, 1-methyl Pentadecanoyl group, 14-methylpentadecanoyl group, 13,13-dimethyltetradecanoyl group, heptadecanoyl group, 15-methylhexadecanoyl group, octadecanoyl group, 1-methylheptadecanoyl group, nonadecanoyl group, Examples thereof include a linear or branched C _1-26 alkyl-carbonyl group such as an icosanoyl group and a henaicosanoyl group.

Examples of the alkenyl-carbonyl group that may have a substituent include a C _2-6 alkenyl-carbonyl group that may have a substituent, such as an acryloyl group, a methacryloyl group, an allylcarbonyl group, and a cinnamoyl group. And so on. Examples of the substituent include an aryl group and the like.

Examples of the alkynyl-carbonyl group include a C _2-6 alkynyl-carbonyl group such as an ethynylcarbonyl group and a propynylcarbonyl group.

Examples of the aryl-carbonyl group include a _C6-18 aryl-carbonyl group such as a benzoyl group, a naphthylcarbonyl group, a biphenylcarbonyl group and an anthranilcarbonyl group.

Examples of the heteroaryl-carbonyl group include non-aromatic or aromatic 5- to 6-membered heteroaryl-carbonyl groups such as 2-pyridylcarbonyl group and thienylcarbonyl group.

Preferred acyl groups are linear or branched C _1-20 alkyl-carbonyl groups, more preferably linear or branched C _1-6 alkyl-carbonyl groups.

R ³ and R ⁴ may be bonded to each other to form a ring together with adjacent nitrogen and carbon atoms. The ring may be selected from the range of, for example, about 4 to 12 membered rings, and is preferably 5 to 10 membered rings.

The repetition number p represents an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.

The double line of the solid line and the broken line indicates a single bond or a double bond, and usually, when R ³ and R ⁴ are bonded to each other to form a ring (heterocycle), it may be a single bond, and R When ³ and R ⁴ do not form a ring (heterocycle), it is often a double bond.

When R ³ and R ⁴ do not form a ring, preferred R ⁴ includes a hydrogen atom, an alkyl group, and an aryl group, and more preferably an alkyl group or an aryl group.

Preferred R ⁵ and / or R ⁶ include a hydrogen atom, an alkyl group, a hydroxyalkyl group and the like.

More specifically, as the heterocyclic compound (guest compound) represented by the formula (2), for example, a compound represented by the following formula (2a) and / or a compound represented by the following formula (2b) can be used. Can be mentioned.

(In the formula, q indicates an integer of 0 to 5; R ³ to R ⁶ and the double line of the solid line and the broken line are the same as those in the above formula (2) including the preferable embodiment).

Further, in the above formula (2a) ^, more preferable embodiments of R3 include a hydrogen atom, a cyanoethyl group and a triazine-alkyl group, and more preferably a hydrogen atom.

In the above formula (2a), more preferable embodiments of ^R4 include a hydrogen atom, a linear or branched C _1-20 alkyl group, and a C _6-14 aryl group, and more preferably linear or branched. It is a branched C _1-12 alkyl group and a C _6-12 aryl group, and among them, a linear or branched C _1-6 alkyl group and a C _6-11 aryl group are preferable. For applications where rapid curability is important, linear or branched C _1-4 alkyl groups, especially C _1-2 alkyl groups, are preferred. Also, C _6-10 aryl groups are preferred for applications where high storage stability is important. Among these, the C _6-10 aryl group is most preferable because it has a particularly excellent balance between rapid curing and high storage stability and can increase the inclusion ratio of the guest compound to 1 mol of the host compound.

In the above formula (2a), more preferable embodiments of R ⁵ include a hydrogen atom, a C _1-8 alkyl group, and a hydroxy C _1-4 alkyl group, and more preferably a hydrogen atom and a C _1-6 alkyl group. It may be present, and among them, a hydrogen atom and a C _1-4 alkyl group are preferable, and a hydrogen atom and a C _1-2 alkyl group are particularly preferable. When R ⁴ is an alkyl group, R ⁵ is often a hydrogen atom or an alkyl group, and when R ⁴ is an aryl group, R ⁵ is often a hydrogen atom.

In the above formula (2a), more preferable embodiments of R ⁶ include a hydrogen atom and a hydroxy C _1-4 alkyl group, and a hydrogen atom is more preferable.

^In the above formula (2a), the type of bond between the carbon atoms to which R5 and R6 are bonded may be a single bond ⁽ imidazoline compound), but it is double because it is industrially easily available. It is preferably a bond (imidazole compound).

In the above formula (2b), the preferred number of repetitions q is an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly an integer of 1 to 3.

Typical examples of the compound represented by the formula (2a) include an imidazoline compound and an imidazole compound, and examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

Examples of the imidazole compound include imidazole; 1-alkyl imidazole such as 1-methylimidazole, 1-ethyl imidazole, 1-n-propyl imidazole, 1-isopropyl imidazole, 1-n-butyl imidazole, 1-isobutyl imidazole; 2 2-alkyl imidazoles such as -methyl imidazole, 2-ethyl imidazole, 2-n-propyl imidazole, 2-isopropyl imidazole, 2-n-butyl imidazole, 2-isobutyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole 2-arylimidazole such as 2-phenylimidazole; 4-alkylimidazole such as 4-methylimidazole, 4-ethylimidazole; 1,2-dialkylimidazole such as 1,2-dimethylimidazole; 2,4-dimethylimidazole, 2,4-Dialkylimidazole such as 2-ethyl-4-methylimidazole; 2-aryl-4-alkylimidazole such as 2-phenyl-4-methylimidazole; 1-aralkyl such as 1-benzyl-2-methylimidazole- 2-alkylimidazole; 1-aralkyl-2-arylimidazole, such as 1-benzyl-2-phenylimidazole; 1-cyanoethyl-2-, such as 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, etc. Alkylimidazole; 1-cyanoethyl-2-arylimidazole such as 1-cyanoethyl-2-phenylimidazole; 1-cyanoethyl-2,4-dialkylimidazole such as 1-cyanoethyl-2-ethyl-4-methylimidazole; 2-phenyl 2-aryl-4-alkyl-5-hydroxyalkylimidazole such as -4-methyl-5-hydroxymethylimidazole; 2-aryl-4,5- such as 2-phenyl-4,5-bis (hydroxymethyl) imidazole Examples include bis (hydroxyalkyl) imidazole.

In many cases, at least one group of R ³ to R ⁶ is a substituent other than a hydrogen atom in the imidazole compound, and preferably at least one group of R ³ to R ⁵ is a substituent other than a hydrogen atom. Yes, more preferably at least one group of R ⁴ or R ⁵ is a substituent other than a hydrogen atom, and more preferably at least R ⁴ is a substituent other than a hydrogen atom.

Typical examples of the compound represented by the formula (2b) (bicyclic amidine compound) include diazabicycloundecene (DBU: 1,8-diazabicyclo [5.4.0] -7-undecene). Examples thereof include diazabicyclononene (DBN: 1,5-diazabicyclo [4.3.0] -5-nonene).

These heterocyclic compounds (guest compounds) can also be used alone or in combination of two or more. Among these heterocyclic compounds, the compound represented by the above formula (2a) is preferable, and the imidazole compound is particularly preferable. Preferred imidazole compounds include 2-alkylimidazole, 2-arylimidazole, 2,4-dialkylimidazole, 1-cyanoethyl-2,4-dialkylimidazole, and more preferably 2-C such as 2-methylimidazole. _1-6 Alkyl-imidazole; 2-C _6-12aryl -imidazole such as 2-phenylimidazole; 2,4-diC _1-6 alkyl-imidazole such as 2-ethyl-4-methylimidazole; 1-cyanoethyl- Examples thereof include 1-cyanoethyl-2,4-diC _1-6 alkyl-imidazole such as 2-ethyl-4-methylimidazole.

In particular, for applications where rapid curability is important, 2-C _1-4 alkyl-imidazole such as 2-methylimidazole; 2,4-diC _1-4 alkyl- imidazole such as 2-ethyl-4-methylimidazole- Imidazole is preferable, more preferably 2-C _1-2 alkyl-imidazole, 2,4-diC _1-2 alkyl-imidazole, and particularly preferably 2-C _1-2 alkyl-imidazole. Further, in applications where high storage stability is important, 2-C _6-10 aryl-imidazole such as 2-phenylimidazole is preferable. Among these, 2-C _6-10 such as 2-phenylimidazole is excellent in that it has an excellent balance between rapid curing and high storage stability and can increase the inclusion ratio of the guest compound to 1 mol of the host compound. Aryl-imidazole is most preferred.

These heterocyclic compounds may be salts with acids such as organic acids such as trimellitic acid, pyromellitic acid, isocyanuric acid or inorganic acids such as hydrochloric acid.

The guest compound is not necessarily necessary, but is not necessary, in addition to the guest compound having a 5- or 6-membered heterocycle containing a plurality of nitrogen atoms as a constituent atom of the ring or a condensed heterocycle thereof (first guest compound). It may contain other guest compounds (or second guest compounds) that do not belong to the category of the first guest compound.

The second guest compound is not particularly limited, and conventional amine compounds such as aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines (provided that the first guest compound is used. ), Modified amines and the like, and specific examples thereof include amine-based compounds exemplified as other curing agents and / or curing accelerators described later. These second guest compounds can also be used alone or in combination of two or more.

The ratio of the first guest compound may be selected from, for example, 10% by mass or more, specifically, about 30 to 100% by mass with respect to the entire guest compound encapsulated in the host compound. The preferred range is, stepwise, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, and the more preferable range is 90% by mass or more, 95% by mass or more, particularly. It is preferably 100% by weight (substantially only the first guest compound). When the second guest compound is contained, the ratio may be, for example, 60 to 99% by mass, preferably 80 to 95% by mass.

The proportion of the guest compound represented by the formulas (2a) and / or (2b) is, for example, 10% by mass or more, specifically, about 30 to 100% by mass with respect to the entire first guest compound. You may select from the range. The preferred range is, stepwise, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, and the more preferable range is 90% by mass or more, 95% by mass or more, particularly. It is 100% by mass (substantially only the guest compound represented by the above formulas (2a) and / or (2b)). When the first guest compound that does not belong to the category of the formula (2a) and / or (2b) is contained, the ratio may be, for example, 60 to 99% by mass, preferably 80 to 95% by mass. good.

In the clathrate compound, the ratio (or clathrate ratio) of the guest compound to 1 mol of the host compound can be selected from, for example, about 0.5 to 10 mol, and the preferable range is 0 in the following steps. It is .8 to 8 mol, 1 to 5 mol, 1.5 to 4.5 mol, and more preferably 2 to 4 mol. Further, in the present invention, since it is easy to greatly adjust the inclusion ratio, the ratio of the guest compound to 1 mol of the host compound is, for example, 2.5 to 6 mol, preferably 3 to 5 mol, and more preferably 3.5 to. It is 4.5 mol.

In the clathrate compound, the phenolic hydroxyl group may form a salt, for example, a salt with a base. In the present invention, the clathrate compound also includes a compound forming such a salt as long as it has a clathrate form.

[Method for producing clathrate compound]
In the present invention, the clathrate compound can be prepared and produced by mixing (or reacting) the host compound represented by the formula (1) with the guest compound containing the first guest compound. It can be obtained by collecting the clathrate.

When at least one component of the host compound and the guest compound is liquid at the mixing temperature, the other component may be added to one component that is liquid and mixed. For example, when the guest compound is a liquid, the host compound may be added to the guest compound. The mixing temperature may be, for example, normal temperature or about 30 to 100 ° C., preferably 50 to 100 ° C., and usually 70 to 90 ° C.

The mixing of the host compound and the guest compound may be carried out in the presence of a solvent, if necessary. As the solvent, typically alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutanol, t-butanol and the like; ethers such as 2-methoxyethanol (or methyl cellosolve). ), Ethylene glycol monoethyl ether (or ethyl cellosolve), cellosolves such as ethylene glycol monobutyl ether (or butyl cellosolve), diethylene glycol monomethyl ether (or methylcarbitol), diethylene glycol monoethyl ether (or ethylcarbitol), diethylene glycol monobutyl ether Carbitols such as (or butyl carbitol), cyclic ethers such as dioxane, tetrahydrofuran, chain ethers such as diethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 2- Chain ketones such as hexanone, cyclic ketones such as isophorone, cyclohexanone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate and the like; ether esters such as, for example. Ethylene glycol monoethyl ether acetate (or ethyl cellosolve acetate), diethylene glycol monoethyl ether acetate (or ethyl carbitol acetate), propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, etc .; aliphatic hydrocarbons such as heptane, Octanes and the like; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, chlorobenzene and the like; amides such as dimethylformamide , Amids such as dimethylacetamide; sulfoxides such as dimethylsulfoxide can be exemplified.

The solvent may be an aprotic polar solvent such as amides and sulfoxides. These solvents can be used alone or as a mixed solvent of two or more kinds. Of these solvents, esters such as ethyl acetate are usually often used.

The mixing ratio of the guest compound to 1 mol of the host compound is, for example, 0.5 to 5 mol, preferably 1 to 4 mol, and more preferably 2 to 3 mol.

Mixing (or reaction) may be carried out with stirring, if necessary. Further, the mixing (or reaction) may be carried out under heating, and the mixing temperature (or heating temperature) is below the boiling point of the solvent, for example, 30 to 120 ° C., preferably 50 to 100 ° C., and is usually 70. Often at ~ 90 ° C. When heated, it may be cooled if necessary and the produced solid may be recovered. The mixing (or reaction) time is not particularly limited, and may be, for example, in the range of about 0.5 minutes to 72 hours, preferably 1 minute to 24 hours, more preferably 5 minutes to 6 hours. More preferably, it is 10 minutes to 2 hours.

When a solvent is used, after the mixing (or reaction) is completed, the solvent may be distilled off by a conventional method such as atmospheric distillation or vacuum distillation, if necessary. Moreover, the clathrate compound may be precipitated by mixing the mixture containing a solvent with a solvent different from the solvent used for the mixing. The recovered clathrate compound may be washed or dried if necessary. As a drying method, vacuum drying is preferable. The drying temperature is, for example, 50 to 100 ° C, preferably 70 to 90 ° C.

The composition ratio (or inclusion ratio) of the host compound and the guest compound in the clathrate compound can be easily determined by a conventional analysis method, for example, the integration ratio of ¹ H-NMR spectrum. It is also possible to determine the composition ratio of the host compound and the guest compound based on the amount of the guest compound released from the clathrate compound with heating by thermogravimetric analysis (TGA). Further, the structure of the clathrate compound can be determined by a method such as single crystal X-ray structure analysis or powder X-ray diffraction. In the present specification and claims, the composition ratio of the host compound and the guest compound of the inclusion compound was determined to be the simplest integer ratio from the result of analysis by ¹ H-NMR spectrum.

[Cursable composition]
In the present invention, the host compound represented by the formula (1) stably encapsulates a predetermined heterocyclic compound that functions as a curing agent and / or a curing accelerator of the epoxy resin (epoxy compound), or the epoxy resin. Even when mixed with, it is stable for a long time at low temperature (normal temperature or storage temperature). On the other hand, the clathrate compound releases the heterocyclic compound upon heating, or when heated to a predetermined temperature, the epoxy resin can be rapidly cured. Further, in the inclusion compound, probably because the heterocyclic compound which is a guest compound has a secondary amino group and / or a tertiary amino group, it functions as a curing agent for an epoxy resin and also as a curing accelerator. It can also be made to work. Therefore, the inclusion compound can be effectively used as a curing agent and / or a curing accelerator for curing the epoxy resin (epoxy compound), and can be used in combination with the epoxy resin (epoxy compound) to prepare a curable composition. It is useful.

(Second curing agent and / or curing accelerator)
The curable composition of the present invention may contain the inclusion compound (also referred to as a first curing agent and / or a curing accelerator) and an epoxy resin, and if necessary, a conventional curing agent for an epoxy resin and a curing agent. / Or a curing accelerator (also referred to as a second curing agent and / or a curing accelerator) may be contained. Such a curing agent is not particularly limited as long as it is a compound that cures the epoxy resin by reacting with the oxylan ring (or epoxy group) of the epoxy resin, and the curing accelerator is also a compound that accelerates the curing reaction of the epoxy resin. If there is, there is no particular limitation. Examples of such a curing agent and / or curing accelerator include amine-based compounds, amide-based compounds, ester-based compounds, phenol-based compounds, alcohol-based compounds, thiol-based compounds, ether-based compounds, thioether-based compounds, and urea-based compounds. Examples thereof include compounds, thiourea compounds, Lewis acid compounds, phosphorus compounds, acid anhydride compounds, onium salt compounds (or cationic polymerization initiators), and active silicon compounds-aluminum complexes.

Specific examples of the second curing agent and / or curing accelerator include the following compounds.

Examples of amine-based compounds include aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, and modified amines.

Examples of aliphatic amines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, pentanediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, and 2,5-dimethyl. Linear or branched alkylenediamines such as -2,5-hexanediamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, pentamethyldiethylenetriamine; dimethylaminopropylamine, N, N-dialkylaminoalkylamines such as diethylaminopropylamine, dibutylaminopropylamine; (poly) etherdiamine such as bis (2-dimethylaminoethyl) ether, diethylene glycol bis (3-aminopropyl) ether, polypropylene glycol diamine Kind: N-, such as N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N', N'-tetramethylpropylenediamine. Alkyl-substituted alkylenediamines; alkanolamines such as dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol; linear or branched alkylamines such as mono-t-alkylamines.

Examples of alicyclic amines include mensendiamine; isophoronediamine; dialkylcycloalkylamines such as dimethylcyclohexylamine; and hydrogenated aromatic amines described later. Examples of hydrogenated aromatic amines include bis (aminocyclohexyl) alkanes such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; 1,2-cyclohexanediamine. , Cyclohexanediamine such as 1,4-cyclohexanediamine; hydrogenated m-xylylene diamine; hydrogenated 1,3,5-tris (aminomethyl) benzene and the like.

Examples of aromatic amines include phenylenediamines such as o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine; Tri (aminomethyl) benzenes; mono-to tri (dialkylaminomethyl) phenols such as 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol; bis (4-aminophenyl) Bis (aminophenyl) alkanes such as methane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3-ethylphenyl) methane; bis (amino) such as bis (4-aminophenyl) sulfone Phenyl) sulfones; phthalocyanine amines such as phthalocyanine tetramine; benzylalkylamines such as benzylmethylamine, benzyldimethylamine, (α-methylbenzyl) methylamine, (α-methylbenzyl) ethylamine and the like.

Heterocyclic amines can be roughly classified into amines having a heterocyclic skeleton containing one nitrogen atom and amines having a heterocyclic skeleton containing a plurality of nitrogen atoms. Examples of amines having a heterocyclic skeleton containing one nitrogen atom include pyridines such as pyridine and picolin; piperidines such as 4-amino-2,2,6,6-tetramethylpiperidine; and pyrrol. Pirols such as 2H-pirol; morpholines such as morpholine, methylmorpholine, ethylmorpholin and the like can be mentioned.

Examples of amines having a heterocyclic skeleton containing a plurality of nitrogen atoms include, for example, a 5- or 6-membered heterocycle containing a plurality of nitrogen atoms exemplified as a constituent atom of the ring or a compound having a condensed heterocycle thereof. And so on. More specifically, for example, monocyclic heterocyclic compounds such as piperazins and triazines exemplified in the section of guest compounds, imidazolines and imidazoles exemplified as the compounds represented by the above formula (2a); guest compounds. Condensed polycyclic heterocyclic compounds such as the triethylenediamines exemplified in the above section and the bicyclic amidine compound exemplified as the compound represented by the above formula (2b); 3,9-bis (3-aminopropyl) -2. , 4,8,10-Tetraoxaspiro [5.5] Spirocyclic amines such as undecane and the like.

Examples of the modified amines include polyamines (or amine adducts) in which amines are added to epoxy compounds, Michael-added polyamines, Mannig-added polyamines, thiourea-added polyamines, ketone-blocking polyamines (ketimine), dicyandiamides, guanidines, and organic acid hydrazides. Examples thereof include diaminomaleonitrile, amineimide, boron trifluoride-piperidin complex, and boron trifluoride-monoethylamine complex.

These amine-based compounds may be salts with an acid, for example, an organic acid such as 2-ethylhexic acid, trimellitic acid, pyromellitic acid, isocyanuric acid or an inorganic acid such as hydrochloric acid.

Examples of the amide-based compound include polyamide (or polyaminoamide) obtained by condensation of dimer acid (polymerized fatty acid or multimerized fatty acid) and polyamine. Examples of the dimer acid include dimers to tetramers of unsaturated higher fatty acids. Examples of the polyamine include alkylenediamine and polyethylene polyamine.

Examples of the ester compound include active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids.

Examples of the phenolic compound include, as a phenolic resin curing agent, an aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin, a novolak-type phenol resin such as phenol novolac resin and cresol novolac resin, and modified resins thereof, for example. , Phenol resins such as epoxidized or butylated novolak type phenolic resins; modified phenolic resins such as dicyclopentadiene-modified phenolic resins, paraxylene-modified phenolic resins, triphenolalcan-type phenolic resins, polyfunctional phenolic resins, etc. It can be exemplified.

Examples of the alcohol-based compound include polyols. Examples of the thiol compound include polymercaptan and the like. Examples of the ether compound include polyether and the like. Examples of the thioether compound include polysulfide and the like. Examples of the urea-based compound include butylated urea and butylated melamine. Examples of the thiourea compound include butylated thiourea. Examples of the Lewis acid-based compound include boron trifluoride.

Examples of the phosphorus-based compound include organic phosphine compounds such as alkylphosphine such as ethylphosphine and butylphosphine, and primary phosphines such as arylphosphine such as phenylphosphine; dialkylphosphine such as dimethylphosphine, dipropylphosphine and methylethylphosphine. Second phosphines such as diarylphosphine such as diphenylphosphine; trialkylphosphines such as trimethylphosphine and triethylphosphine, and third phosphines such as triarylphosphine such as triphenylphosphine can be mentioned.

Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimeritate), and glycerol tris (anhydrotrimeritate). Aromatic polycarboxylic acid anhydrides such as: tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexentricarboxylic anhydride, 5-( 2,5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, hymic anhydride, methyl hymic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalanhydride Alicyclic polycarboxylic acid anhydrides such as acid (methylnagic anhydride); maleic anhydride, tetramethylene maleic anhydride, dodecenyl anhydride succinic acid, polyazipic acid anhydride, polyazereic acid anhydride, polysevacinic acid anhydride, poly Alipid polycarboxylic acid anhydrides such as (ethyloctadecanedioic acid) anhydrides and poly (phenylhexadecanedioic acid) anhydrides; halogens such as hetic anhydride (chlorendic anhydride), tetrabromophthalic anhydride, tetrachlorophthalic anhydride Examples include acid anhydride.

Examples of the onium salt-based compound include aryldiazonium salt, diaryliodonium salt, arylsulfonium salt, arylmethylsulfonium salt, diarylsulfonium salt, triarylsulfonium salt and the like. Arylmethyl sulfonium salts and the like are often used, and examples thereof include benzylmethyl sulfonium salts.

Examples of the active silicon compound-aluminum complex include triphenylsilanol-aluminum complex, triphenylmethoxysilane-aluminum complex, silylperoxide-aluminum complex, and triphenylsilanol-tris (salicil aldehyde) aluminum complex.

These second curing agents and / or curing accelerators can be used alone or in combination of two or more. The ratio of the clathrate compound (first curing agent and / or curing accelerator) to the second curing agent and / or curing accelerator is, for example, the former / the latter (mass ratio) = 100/0 to 30/70, preferably 100/0 to 50/50, more preferably 100/0 to 70/30, even more preferably 100/0 to 90/10, especially 100/0 (substantially only the clathrate compound). Is preferable.

When the second curing agent and / or curing accelerator is used, the ratio of the functional group capable of reacting with the epoxy group in the second curing agent and / or the curing accelerator is the ratio of the functional group capable of reacting with the epoxy group to the epoxy group in the epoxy resin. For example, it is 0.7 to 1.3 equivalents, preferably 0.8 to 1.2 equivalents, more preferably 0.9 to 1.1 equivalents, and usually 1 equivalent. Examples of the functional group capable of reacting with the epoxy group include an amino group, an acid anhydride group, a hydroxyl group and the like.

(Epoxy resin)
The epoxy resin (or epoxy compound) may be, for example, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, an epoxy resin obtained by oxidizing an unsaturated double bond to epoxidize, or the like. ..

Examples of the glycidyl ether type epoxy resin (or compound) include glycidyl ethers of alcan monools, polyglycidyl ethers of alcan polyols, polyglycidyl ethers of mononuclear polyhydric phenols or alkylene oxide adducts thereof, and polynuclear polyvalent. Examples thereof include polyglycyl ethers of phenols or alkylene oxide adducts thereof, and polyglycyl ethers of heterocyclic compounds.

Examples of glycidyl ethers of alkane monools include phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, s-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, and stearyl glycidyl ether. And so on.

In the polyglycidyl ether of alcan polyols, examples of the alcan polyols include ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiethylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol. And so on.

In the polyglycidyl ether of mononuclear polyhydric phenols or an alkylene oxide adduct thereof, examples of the mononuclear polyhydric phenols include hydroquinone, resorcinol, pyrocatechol, fluoroglucosinol and the like.

In the polyglycyl ether of polynuclear polyphenols or alkylene oxide adducts thereof, the polynuclear polyphenols include, for example, dihydroxynaphthalene, biphenol, bisphenol, tris or tetrakis (hydroxyphenyl) alkane, novolak or novolak resin, and the like. Examples include terpenphenol.

Examples of bisphenols include methylene bisphenol (or bisphenol F), methylenebis (orthocresol), etylidene bisphenol (or bisphenol AD), isopropyridene bisphenol (or bisphenol A), isopropyridenebis (orthocresol), tetrabromobisphenol A. , 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, bis (hydroxyphenyl) ketone, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) thioether, Examples thereof include bis (hydroxyphenyl) sulfone (or bisphenol S) and 9,9-bis (hydroxyaryl) fluorene. Examples of 9,9-bis (hydroxyaryl) fluorene include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis. (4-Hydroxy-3,5-dimethylphenyl) fluorene ,, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9, Examples thereof include 9-bis (5-hydroxy-1-naphthyl) fluorene.

Examples of the alkylene oxide adduct include an adduct of C _2-4 alkylene oxide such as ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is not particularly limited, and is, for example, 1 to 20 mol, preferably 2 to 10 mol, relative to 1 mol of the phenols.

Examples of the tris or tetrakis (hydroxyphenyl) alkane include 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like.

Examples of the novolak or novolak resin include phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak and the like.

Examples of the polyglycyl ether of the heterocyclic compound include triglycidyl isocyanurate.

Examples of the glycidyl ester type epoxy resin (or compound) include monoglycidyl esters of monocarboxylic acids such as versatic acid glycidyl ester; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, Fat groups such as azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylene tetrahydrophthalic acid. , Glycidyl esters of alicyclic or aromatic polyvalent carboxylic acids; homopolymers or copolymers of glycidyl (meth) acrylate and the like.

Examples of the glycidylamine type epoxy resin (or compound) include N, N-diglycidylaniline, bis [4- (N-methyl-N-glycidylamino) phenyl] methane, N, N-diglycidyl toluidine, and tetraglycidyl. Examples thereof include diaminodiphenylmethane and triglycidylaminophenol.

Examples of the epoxy compound in which the unsaturated double bond is epoxidized include vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-. Epoxides of cyclic olefins such as 6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, etc. Examples include the epoxidized conjugated diene polymer of.

These epoxy resins (or compounds) can be used alone or in combination of two or more. The epoxy resin (or compound) may be a monomer or may contain a multimer of about a dimer to a decamer. Further, mono or polyglycidyl ethers of alkane monools or alkane polyols, glycidyl esters of monocarboxylic acids, epoxidized products of cyclic olefins and the like are often used as reactive diluents.

Preferred epoxy resins include polyglycidyl ethers having multiple epoxy groups (or oxylan rings) in the molecule, such as methylenebisphenol (or bisphenol F), methylenebis (orthocresol), etylidenebisphenol (or bisphenol AD), isopropyridene. Examples thereof include bisphenols such as bisphenol (or bisphenol A), isopropylidenebis (orthocresol), 9,9-bis (hydroxyaryl) fluorene, or polyglycidyl ether as an alkylene oxide adduct thereof.

Further, the epoxy resin may be a liquid having fluidity at about room temperature, for example, 10 to 30 ° C., preferably 15 to 20 ° C., or a highly viscous (or highly viscous) semi-solid or solid with poor fluidity. Often, it is usually a liquid epoxy resin that has fluidity at a temperature (mixing temperature or processing temperature) at which it is mixed with the inclusion compound, and may be liquid or viscous at the mixing temperature.

In the curable composition of the present invention, the proportion of the clathrate compound can be appropriately selected depending on the curing method, and the heterocyclic compound as the first guest compound is usually used as a curing agent and / or a curing accelerator. It may be a ratio. For example, the first guest compound or heterocyclic compound (first curing agent and / or curing accelerator) is always incorporated into the curing resin by a covalent bond by the reaction with the epoxy group in the epoxy resin. In the case of an agent, the ratio of the inclusion compound is usually 0.1 to 1 in terms of the inclusion heterocyclic compound with respect to 1 mol of the epoxy group (or oxylan ring), depending on the characteristics of the cured resin. It can be selected from the range of about mol, preferably 0.2 to 0.8 mol, and more preferably 0.25 to 0.5 mol.

Further, a polymerization type curing agent or a photo-initiated curing type in which the heterocyclic compound is not incorporated into the cured resin by a covalent bond but catalytically induces ring opening of the epoxy group to cause a polymerization addition reaction between the epoxy compounds. When it is an agent or used as a curing accelerator, the ratio of the inclusion compound is about 1 mol or less in terms of the included heterocyclic compound with respect to 1 mol of the epoxy group (or oxylan ring). It can be selected from the range of 0.001 to 0.5 mol, more preferably 0.005 to 0.1 mol.

Usually, the ratio of the inclusion compound in the curable composition is such that the heterocyclic compound (first guest compound) in the inclusion compound is 0.1 to 25 parts by mass with respect to 100 parts by mass of the epoxy resin. The ratio is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and particularly 1.5 to 5 parts by mass.

The curable composition of the present invention can be produced by mixing a curing agent and / or a curing accelerator component containing the clathrate compound with an epoxy resin. For example, a curing agent and / or a curing accelerator component containing the inclusion compound and an epoxy resin are mixed with a homogenizer, a mixer or a mixer, a kneader such as a kneader, a roll, or an extruder, or a raft machine (crusher). It may be prepared by mixing or kneading at a temperature and time at which a curing reaction (or gelation) does not occur or can be suppressed by using the above. The kneading may be, for example, melt kneading.

Further, mixing or kneading may be carried out under heating, for example, at about 50 to 100 ° C., but mixing or kneading at a low temperature, for example, about 0 to 50 ° C., preferably in an ice bath, and mixing under heating. Alternatively, kneading is often omitted. In addition, you may mix or knead in the presence of the solvent exemplified in the section of the manufacturing method of the clathrate compound.

The curable composition of the present invention may contain various additives such as silane coupling agents, plasticizers, organic solvents, reactive diluents, fillers, reinforcing agents, colorants such as pigments, as required. Stabilizers such as flame retardants, mold release agents, antioxidants, UV absorbers, bulking agents, thickeners and the like may be added.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3 -(Meta) acryloyloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane And so on.

Examples of the plasticizer include an alkandicarboxylic acid-based plasticizer such as a phthalic acid-based plasticizer and an adipic acid-based plasticizer, a phosphoric acid ester-based plasticizer, and a polyester-based plasticizer.

Examples of the organic solvent include the solvents exemplified in the section of the method for producing the clathrate compound. Examples of the reactive diluent include the above-exemplified epoxy compounds, for example, epoxy compounds such as n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butyl phenyl glycidyl ether, and dicyclopentadiene diepoxide, phenol, cresol, and t. -Phenols such as butylphenol can be mentioned.

Examples of the filler include metal carbonates such as calcium carbonate; metal oxides such as silica, titanium oxide and zinc oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal sulfates such as barium sulfate; Metal borates such as aluminum borate; metal titanates such as potassium titanate; minerals such as talc, kaolin, clay, mica, wollastonite, sepiolite, zonotrite and the like. Examples of calcium carbonate include calcium bicarbonate and light calcium carbonate. Examples of silica include natural silica, synthetic silica, and fused silica.

Reinforcing agents can be roughly classified into, for example, organic fibers and inorganic fibers. Examples of the organic fiber include natural fibers such as cellulose fibers and cellulose nanofibers; synthetic fibers such as polyalkylene allylate fibers, vinylon fibers and aramid fibers. Examples of the inorganic fiber include glass fiber and carbon fiber.

The colorant may be any of black pigments such as carbon black, white pigments such as titanium oxide, yellow pigments, orange pigments, red pigments, purple pigments, blue pigments, green pigments and the like.

Examples of flame retardants include hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyloxide, and bis (pentabromo) phenylethane. , Tris (tribromophenoxy) triazine, ethylenebistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, brominated products such as polypentabromobenzyl acrylate, triphenyl phosphate, tri Cresyl phosphate, trixinyl phosphate, cresil diphenyl phosphate, xylyl diphenyl phosphate, cresil bis (di-2,6-xylenyl) phosphate, 2-ethylhexyldiphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate , Bisphenol A bis (dicresyl) phosphate, resorcinol bis (di-2,6-xylenyl) phosphate, tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromopropyl) phosphate, Phenyl esters such as diethyl-N, N-bis (2-hydrooxyethyl) aminomethylphosphonate, anionic oxalic acid-treated aluminum hydroxide, nitrate-treated aluminum hydroxide, high-temperature hot water-treated aluminum hydroxide, tinic acid surface treatment Examples thereof include a metal hydrate compound, a nickel compound surface-treated magnesium hydroxide, a silicone polymer surface-treated magnesium hydroxide, procobite, a multilayer surface-treated hydrated metal compound, and a cationic polymer-treated magnesium hydroxide.

Examples of the release agent include fatty acid release agents such as higher fatty acids, higher fatty acid esters, and higher fatty acid calcium; waxes such as carnauba wax and polyethylene wax; silicone oil and the like.

Further, the curable composition of the present invention may contain an elastomer (or an elastomer modifier) in addition to the epoxy resin, if necessary. Examples of the elastomer (or elastomer modifier) include acrylonitrile butadiene rubber (NBR), liquid polybutadiene, polybutadiene (butadiene rubber, BR), chloroprene rubber, silicone rubber, modified silicone rubber, crosslinked NBR, crosslinked BR, and acrylic rubber (crosslinked NBR). (Including core-shell type acrylic rubber), urethane rubber, polyester elastomer, functional group-containing liquid NBR, liquid polyester, liquid polysulfide, urethane prepolymer and the like.

Further, the curable composition may contain another resin (or a second resin) in addition to the epoxy resin, if necessary. Examples of the second resin include high-density polyethylene, olefin resins such as polypropylene, styrene resins such as polystyrene, acrylic resins such as polymethylmethacrylate, halogen-containing resins such as polyvinyl chloride, and polyethylene terephthalates. Examples thereof include polyester resins, polycarbonate resins, polyamide resins such as nylon 6 and nylon 66, polyurethane resins, and silicone resins. The second resin may be an engineering plastic such as polybutylene terephthalate, polyethylene naphthalate, bisphenol A type polycarbonate, polyacetylate, polysulfone, polyethersulfone, polyetherimide, or polyetheretherketone.

These additives, elastomers, and resins can be used alone or in combination of two or more. The proportions of these additives, elastomers and / or resins are not particularly limited and can be appropriately selected depending on the intended use.

The present invention also includes a cured product obtained by curing the curable composition. Such a cured product can be prepared by heating and curing the curable composition, depending on the use of the curable composition. For example, the curable composition may be applied to a base material and cured, may be injected or sealed in a predetermined portion and cured, may be cast and cured, a fiber base material or the like. A prepreg may be prepared by impregnating the base material of the above material, and the prepreg may be laminated by a method such as superposition or winding, formed into a predetermined shape, and cured. The heating temperature in curing may be, for example, about 100 to 250 ° C., preferably 110 to 200 ° C., and more preferably 120 to 180 ° C. Further, since the curable composition of the present invention can be cured quickly even at a relatively low temperature, a preferable heating temperature is 100 to 160 ° C, more preferably 120 to 150 ° C, and most preferably 130 to 140 ° C. Is.

The gelation time of the curable composition of the present invention can be selected from a range of, for example, about 30 minutes or less at a heating temperature of 100 ° C., and the preferred range is 25 minutes or less, 20 minutes or less in the following steps. , 15 minutes or less, more preferably 10 minutes or less. The gelation time is, for example, 0.1 to 15 minutes, preferably 1 to 10 minutes.

Although the curable composition of the present invention can be cured quickly at a low temperature, it has surprisingly high storage stability (or storage stability). Therefore, the viscosity at 25 ° C. after preparing the curable composition and storing it in a sealed container at 25 ° C. for 24 hours is, for example, relative to the initial viscosity at 25 ° C. immediately after preparing the curable composition (0 hours after preparation). It is 1 to 2.5 times, and the preferable range is 2.1 times or less, 2 times or less, 1.8 times or less, 1.5 times or less, and more preferably 1.4 times. It is less than or equal to, and 1.3 times or less is most preferable.

In the present specification and claims, the gelation time and viscosity can be measured by the method described in Examples described later.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following examples and comparative examples, various characteristics were measured as follows.

( ^{1 1} H-NMR)
In ¹ H-NMR, the clathrate compound was dissolved in deuterated chloroform, deuterated methanol, deuterated dimethylsulfoxide, etc., and measured using "AVANCE III HD" ( ¹ H resonance frequency: 300 MHz) manufactured by Bruker Biospin.

(XRD)
X-ray diffraction (XRD) was measured using "SMART LAB" (X-ray source: Cu Kα) manufactured by Rigaku Corporation.

(TGA)
Thermogravimetric analysis (TGA) was measured using "TGA 4000" manufactured by PerkinElmer Co., Ltd.

1. 1. Preparation of Clathrate Compound [Example 1] (BINOL: Synthesis of Clathrate Compound of 2E4MZ)
2-Ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemicals Corporation) in a solution of 1,1'-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) in ethyl acetate (100 g) at 80 ° C. , 13.2 g, 120 mmol) in ethyl acetate (50 g) was added. After stirring for 1 hour, heating was stopped and the mixture was cooled to 10 ° C., and the resulting solid was collected by filtration and dried to obtain a product (white solid, yield 23.6 g). FIGS. 6, 11 and 20 show the measurement results of ¹ H-NMR, XRD and TGA of the obtained clathrate compound. It was confirmed by XRD that it was a crystalline compound different from BINOL alone. Further, it was confirmed by ^{1 1} H-NMR that the obtained clathrate compound was a clathrate compound having a clathrate ratio of BINOL: 2E4MZ = 1: 2. Furthermore, it was supplementarily confirmed from TGA that the inclusion ratio was the same as described above. For comparison, the measurement results of ¹ H-NMR, XRD and TGA of BINOL alone are shown in FIGS. 1, 10 and 15, and the measurement results of ¹ H-NMR and TGA of 2E4MZ alone are shown in FIGS. 2 and 16, respectively. ..

In the TGA chart of the clathrate compound obtained in the examples, the two broken lines drawn parallel to the horizontal axis (temperature) indicate the start of measurement and the completion of guest release, and “ΔY” indicates the clathrate. The mass ratio of the guest compound in the contact compound is shown (hereinafter, the same applies).

[Example 2] (BINOL: Synthesis of clathrate compound of 2MZ-H)
1,1'-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) with 2-methylimidazole (2MZ-H, manufactured by Shikoku Kasei Kogyo Co., Ltd., 9.9 g, 120 mmol) and ethyl acetate (50 g). Was added and dissolved at 80 ° C. After stirring for 1 hour, heating was stopped and the mixture was cooled to 10 ° C., and the resulting solid was collected by filtration and dried to obtain a product (white solid, yield 16.7 g). Figures 7, 12 and 21 show the measurement results of ¹ H-NMR, XRD and TGA of the clathrate compounds obtained. It was confirmed by XRD that it was a crystalline compound different from BINOL alone. Further, it was confirmed by ¹ H-NMR that the obtained clathrate compound was a clathrate compound having a clathrate ratio of BINOL: 2MZ-H = 1: 2. Furthermore, it was supplementarily confirmed from TGA that the inclusion ratio was the same as described above. For comparison, the measurement results of ¹ H-NMR, XRD and TGA of BINOL alone are shown in FIGS. 1, 10 and 15, and the measurement results of ¹ H-NMR and TGA of 2MZ-H alone are shown in FIGS. 3 and 17. Each is shown.

[Example 3] (BINOL: Synthesis of clathrate compound of 2E4MZ-CN)
1,1'-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) and 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN, manufactured by Shikoku Kasei Kogyo Co., Ltd., 19.6 g, 120 mmol) ) And ethyl acetate (150 g) were added, and the mixture was stirred at 80 ° C. for 1 hour to dissolve. After stirring, heating was stopped, and after cooling to 10 ° C., the resulting solid was collected by filtration and dried to obtain a product (white solid, yield 26.0 g). Figures 8, 13 and 22 show the measurement results of ¹ H-NMR, XRD and TGA of the clathrate compounds obtained. It was confirmed by XRD that it was a crystalline compound different from BINOL alone. Further, it was confirmed by ^{1 1} H-NMR that the obtained clathrate compound was a clathrate compound having a clathrate ratio of BINOL: 2E4MZ-CN = 1: 2. Furthermore, it was supplementarily confirmed from TGA that the inclusion ratio was the same as described above. For comparison, the measurement results of ¹ H-NMR, XRD and TGA of BINOL alone are shown in FIGS. 1, 10 and 15, and the measurement results of ¹ H-NMR and TGA of 2E4MZ-CN alone are shown in FIGS. 4 and 18. Each is shown.

[Example 4] (BINOL: Synthesis of clathrate compound of 2PZ-PW)
1,1'-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) with 2-phenylimidazole (2PZ-PW, manufactured by Shikoku Kasei Kogyo Co., Ltd., 17.3 g, 120 mmol) and ethyl acetate (475 g). Was added and dissolved at 80 ° C. After stirring for 15 minutes, heating was stopped, and after cooling to 10 ° C., the resulting solid was collected by filtration and dried to obtain a product (white solid, yield 12.0 g). The obtained clathrate compounds show the measurement results of ¹ H-NMR, XRD and TGA of the obtained clathrate compounds in FIGS. 9, 14 and 23. It was confirmed by XRD that it was a crystalline compound different from BINOL alone. Further, it was confirmed by ^{1 1} H-NMR that the obtained clathrate compound was a clathrate compound having a clathrate ratio of BINOL: 2PZ-PW = 1: 4. Furthermore, it was supplementarily confirmed from TGA that the inclusion ratio was the same as described above. For comparison, the measurement results of ¹ H-NMR, XRD and TGA of BINOL alone are shown in FIGS. 1, 10 and 15, and the measurement results of ¹ H-NMR and TGA of 2PZ-PW alone are shown in FIGS. 5 and 19. Each is shown.

Table 1 below shows the composition of each clathrate compound.

2. Preparation and Testing of Curable Composition [Example 5]
Add 6.9 parts by mass of BINOL: 2E4MZ (3 parts by mass as 2E4MZ) to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and homogenizer (manufactured by Nissei Tokyo Office, Ace Homogenizer AM). In -10), the mixture was stirred in an ice bath at a rotation speed of 15000 rpm for 15 minutes to prepare a curable composition.

[Example 6]
Add 4.5 parts by mass of BINOL: 2PZ-PW (3 parts by mass as 2PZ-PW) to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and homogenizer (manufactured by Nissei Tokyo Office Co., Ltd.). , Ace homogenizer AM-10) was stirred in an ice bath at a rotation speed of 15000 rpm for 15 minutes to prepare a curable composition.

[Example 7]
Add 8.2 parts by mass of BINOL: 2MZ-H (3 parts by mass as 2MZ-H) to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and homogenizer (manufactured by Nissei Tokyo Office Co., Ltd.). , Ace homogenizer AM-10) was stirred in an ice bath at a rotation speed of 15000 rpm for 15 minutes to prepare a curable composition.

[Comparative Example 1]
Add 3 parts by mass of 2E4MZ to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and use a homogenizer (Ace Homogenizer AM-10, manufactured by Nissei Tokyo Office Co., Ltd.) to ice at a rotation speed of 15,000 rpm. The mixture was stirred in the bath for 15 minutes to prepare a curable composition.

[Comparative Example 2]
Add 3 parts by mass of 2PZ-PW to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and use a homogenizer (Ace Homogenizer AM-10, manufactured by Nissei Tokyo Office Co., Ltd.) at 15,000 rpm. The mixture was stirred in an ice bath for 15 minutes to prepare a curable composition.

[Measurement of gelation time]
A glass sample tube and an aluminum block having a hole with the same diameter as the outer diameter were prepared. The aluminum block was preheated to a predetermined temperature on a hot plate. Take the sample (curable composition) in the sample tube, insert the sample tube into the hole of the aluminum block, and stir the inside of the sample tube in a circle (in a circular motion) at a speed of about 60 times per minute with a spatula. The time taken from the insertion of the sample tube to the end point was measured with the point where the sample became gel-like and did not adhere to the spatula or the point where the stringing disappeared as the end point. The results are shown in Table 2 below.

[Storage stability test of curable composition]
The initial viscosity of the prepared curable composition (viscosity at 25 ° C. measured 0 hours after preparation, mPa · s / 25 ° C.) was measured using an E-type viscometer (“TVE-22L” manufactured by Toki Sangyo Co., Ltd.). Was measured. Next, the prepared curable composition was stored at 25 ° C. in a closed container, and the viscosity after storage for 24 hours was measured in the same manner. The results are shown in Table 3 below.

The viscosity of the curable composition of Example 5 reached about 2.1 times the initial viscosity after storage for 24 hours, whereas the viscosity of the curable composition of Comparative Example 1 reached about 6 times. The viscosity of the curable composition of Example 6 reached about 1.3 times the initial viscosity after storage for 24 hours, whereas the viscosity of the curable composition of Comparative Example 2 reached about 2.9 times.

Since the curable composition of the present invention contains a predetermined clathrate compound as a curing agent and / or a curing accelerator, it has high storage stability (or storage stability) and exhibits a property of being rapidly cured by heating. Therefore, the curable composition of the present invention has various uses to which an epoxy resin is applied, such as an insulating material, a sealing material, an epoxy resin laminated board, a composite material, a casting material, a repair material for a concrete structure, and an adhesive. It can be used as an agent, coating agent, etc.

Examples of the encapsulating material include encapsulating materials for electronic components such as semiconductors and light emitting diodes. Examples of the epoxy resin laminated board include a laminated board of a base material such as glass cloth, paper, synthetic fiber cloth, and copper foil and an epoxy resin, and specifically, a laminated board for a printed wiring board. Examples of the composite material include a fiber-reinforced composite material with reinforcing fibers such as glass fiber, carbon fiber, and aramid fiber. Examples of the coating agent include varnish, paint (including powder paint), ink and the like.

Claims (7)

A curable composition containing an epoxy resin and a clathrate compound as a curing agent and / or a curing accelerator, wherein the clathrate compound has the following formula (1).

(In the formula, R ¹ and R ² are independently alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen. Atomic, nitro group, cyano group or substituted amino group , m each independently indicates an integer of 0 to 4, and n independently indicates an integer of 0 to 2).
A curable composition comprising a host compound represented by (2) and a guest compound containing at least one imidazole compound selected from 2-arylimidazole and 1-cyanoethyl-2,4-dialkylimidazole . The curable composition according to claim 1, wherein in the formula (1) , m is an integer of 0 to 2 and n is 0 or 1. The curable composition according to claim 1 or 2 , wherein the clathrate compound contains 0.5 to 5 mol of the guest compound with respect to 1 mol of the host compound. The curable composition according to any one of claims 1 to 3 , wherein the epoxy resin is a liquid epoxy resin. The curable composition according to any one of claims 1 to 4 , wherein the guest compound in the clathrate compound is contained in a ratio of 0.1 to 25 parts by mass with respect to 100 parts by mass of the epoxy resin. A clathrate containing the host compound represented by the formula (1) according to claim 1 and a guest compound containing at least one imidazole compound selected from 2-arylimidazole and 1-cyanoethyl-2,4-dialkylimidazole. The method for producing a curable composition according to any one of claims 1 to 5 , wherein the contact compound is mixed with an epoxy resin. A cured product obtained by curing the curable composition according to any one of claims 1 to 5 .

Images