JP2019210325A - Curable composition and its cured product - Google Patents

Abstract

To provide a novel curable composition containing an inclusion compound having 1,1'-bi-2-naphthol compound as a host compound, as a curing agent and/or a curing accelerator of a resin, and its production method and a cured product of the curable composition.SOLUTION: A 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 contains a host compound expressed by the following formula (1) and a guest compound having a 5- or 6-membered heterocyclic ring or its condensed heterocyclic ring containing a plurality of nitrogen atoms as a constituent atom of a ring. (In the formula, Rand Reach is independently a substituent group, ms each is independently an integer of 0 to 4, ns each is independently an integer of 0 to 2.)SELECTED DRAWING: None

Description

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

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

  For example, a 1,1′-bi-2-naphthol compound is known to function as a host compound capable of including a small molecule, and International Publication No. 2008/053496 (Patent Document 1) and International Publication No. In 2010/07954 (Patent Document 2), a method of splitting an optically active substance by forming a diastereomeric salt by inclusion of a racemate in 1,1′-bi-2-naphthol is proposed. 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 Laid-Open No. 11-71449 (Patent Document 3) discloses that a predetermined alkanetetrakisphenol such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane as a host compound and imidazoles as a guest It has been proposed to use an inclusion compound as a compound as a curing agent or curing accelerator for an epoxy resin.

  However, these documents do not describe any use of an inclusion compound containing a 1,1′-bi-2-naphthol compound as a host compound as a resin curing agent.

International Publication No. 2008/053496 International Publication No. 2010/0795504 JP-A-11-71449

  Accordingly, an object of the present invention is to provide a novel curable composition containing an inclusion compound containing a 1,1′-bi-2-naphthol compound as a host compound as a resin curing agent and / or curing accelerator, and its production. It is in providing the method and the hardened | cured material of the said curable composition.

  Another object of the present invention is to provide a curable composition having high storage stability and capable of being 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 provide a curable composition capable of reducing the amount of use even when an inclusion compound is used as a curing agent and / or a curing accelerator, a method for producing the same, and a cured product of the curable composition. It is to provide.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an inclusion compound containing a 1,1′-bi-2-naphthol compound as a host compound is effective as a resin curing agent and / or curing accelerator. The present invention has been completed.

  That is, the curable composition of the present invention includes 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): And a guest compound having a 5- or 6-membered heterocyclic ring containing a plurality of nitrogen atoms as ring constituent atoms or a condensed heterocyclic ring thereof.

(Wherein R ¹ and R ² are each independently a substituent, m is each independently an integer of 0 to 4, and n is each independently an integer of 0 to 2).

In the 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, a halogen atom. An atom, a nitro group, a cyano group, or a substituted amino group may be sufficient, m may be an integer of 0-2, 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 represent a hydrogen atom, a halogen atom, or a nitro group. 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; and R ³ and R ⁴ are bonded to each other to form an adjacent nitrogen atom and You may form a ring with a carbon atom; p shows the integer of 0-3; the double line of a solid line and a broken line shows a single bond or a double bond).

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

(In the formula, q represents an integer of 0 to 5; R ^{3 to} R ⁶ and a double line of a solid line and a broken line are the same as those in the formula (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 a guest compound in a ratio of 0.5 to 5 mol with respect to 1 mol of the host compound. The epoxy resin may be a liquid epoxy resin. The said curable composition may contain the clathrate compound in the ratio of 0.1-25 mass parts with respect to 100 mass parts of epoxy resins.

  The present invention provides an inclusion compound comprising a host compound represented by the above formula (1) and a guest compound having a 5- or 6-membered heterocyclic ring containing a plurality of nitrogen atoms as ring constituent atoms or a condensed heterocyclic ring thereof. And a method for 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 the present specification and claims, the number of carbon atoms of the substituent may be indicated by C ₁ , C ₆ , C ₁₀ or the like. For example, an alkyl group having 1 carbon atom is represented by “C ₁ alkyl”, and an aryl group having 6 to 10 carbon atoms is represented by “C _6-10 aryl”.

  In the present invention, a novel curable composition comprising an inclusion compound containing a 1,1′-bi-2-naphthol compound as a host compound as a resin curing agent and / or curing accelerator can be provided. Moreover, since the said curable composition contains the said inclusion compound, it has high storage stability and can be hardened | cured rapidly by heating. Furthermore, in the present invention, since the molecular weight of the host compound is not so large and the inclusion ratio of the guest compound to 1 mol of the host compound is large, the inclusion compound which is likely to be used in a large amount is usually used as a curing agent and / or curing accelerator Despite being used as a product, its usage 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 2MZ-H. FIG. 4 is a ¹ H-NMR spectrum of 2E4MZ-CN. FIG. 5 is a ¹ H-NMR spectrum of 2PZ-PW. 6 is a ¹ H-NMR spectrum of the clathrate compound of Example 1. FIG. FIG. 7 is a ¹ H-NMR spectrum of the clathrate compound of Example 2. FIG. 8 is the 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. 12 is an XRD chart of the clathrate compound of Example 2. FIG. 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 BINOL TGA chart. FIG. 16 is a TGA chart of 2E4MZ. FIG. 17 is a 2MZ-H TGA chart. FIG. 18 is a TGA chart of 2E4MZ-CN. FIG. 19 is a 2PZ-PW TGA chart. 20 is a TGA chart of the clathrate compound of Example 1. FIG. 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. 23 is a TGA chart of the clathrate compound of Example 4. FIG.

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

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

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

(Wherein R ¹ and R ² are each independently a substituent, m is each independently an integer of 0 to 4, and n is each independently an integer of 0 to 2).

In the 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 a halogen atom, a nitro group, a cyano group, a hydrocarbon group, a group —OR ¹⁰ , Group —SR ¹⁰ , group —COOR ¹⁰ , group —COR ¹⁰ , group —CON (R ¹⁰ ) ₂ (in each formula, R ¹⁰ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, Indicates a group etc.)
You can choose from a wide range. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Typical R ¹ and R ² include, for example, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a 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 linear or branched C _1-10 alkyl such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. A group, preferably a linear or branched C _1-6 alkyl group, more preferably a linear or branched C _1-4 alkyl group.

Examples of the cycloalkyl group include C _5-10 cycloalkyl groups 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 C _6-12 aryl groups such as a phenyl group, a biphenyl group, and a naphthyl group.

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

  The hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, and 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 linear or branched C _1-10 alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group and t-butoxy group, preferably C _1-8. Examples thereof include an alkoxy group, more preferably a C _1-6 alkoxy group.

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

Examples of the aryloxy group include C _6-10 aryloxy groups 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 C _6-10 arylthio groups 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 C _1-4 alkoxy-carbonyl groups such as a methoxycarbonyl group.

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

Examples of the substituted amino group include a dialkylamino group and a bis (alkylcarbonyl) amino group. Examples of the dialkylamino group include a _diC1-4 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.

In the case of having substituents R ¹ and R ² , preferred substituents R ¹ and R ² are alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl Group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group; more preferably, an alkoxy group such as an alkyl group, an aryl group, or a linear or branched C _1-6 alkoxy group And more preferably an alkyl group or an aryl group. Particularly preferred is a linear or branched C _1-6 alkyl group, or a C _6-12 aryl group. Among them, a linear or branched C _1-4 alkyl group such as a methyl group, or phenyl C _6-10 aryl groups such as groups.

The substitution number m of the substituent R ¹ may be, for example, an integer of about 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, especially 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 R ¹ substituted on two different naphthalene rings may be the same or different from each other. When m is 2 or more, the two or more types of R ¹ substituted on the same naphthalene ring may be the same or different from each other.

The substitution number n of the substituent R ² 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 substituted on two different naphthalene rings may be the same or different from each other. In addition, when n is 2, the two types of R ² substituted on the same naphthalene ring may be the same or different from each other.

  A typical example of the compound represented by the formula (1) is 1,1'-bi-2-naphthol (BINOL).

(Guest compound)
The inclusion compound includes, as a guest compound, a predetermined heterocyclic compound, that is, a compound having a 5- or 6-membered heterocyclic ring containing a plurality of nitrogen atoms as ring constituent atoms or a condensed heterocyclic ring 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, particularly 2 It is. The 5- or 6-membered heterocyclic ring may be either an aliphatic heterocyclic ring (or a non-aromatic heterocyclic ring) or an aromatic heterocyclic ring. In addition, the 5- or 6-membered heterocyclic ring may be condensed with an aliphatic or aromatic hydrocarbon ring or any other heterocyclic ring to form the condensed heterocyclic ring.

  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. And a condensed polycyclic heterocyclic compound. As piperazine, for example, piperazine; N, N′-dialkylpiperazine such as N, N′-dimethylpiperazine; N-aminoalkylpiperazine such as N- (aminoethyl) piperazine; 1- (2-dimethylaminoethyl) And N-dialkylaminoethyl-N′-alkylpiperazines such as -4-methylpiperazine. Examples of the triazines include triazine, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, and the like.

  Although the heterocyclic compound (or guest compound) may contain the said compound, it is preferable that the compound represented by following formula (2) is included.

(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 represent a hydrogen atom, a halogen atom, or a nitro group. 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; and R ³ and R ⁴ are bonded to each other to form an adjacent nitrogen atom and You may form a ring with a carbon atom; p shows the integer of 0-3; the double line of a solid line and a broken line shows a single bond or a double bond).

In the 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 group. Examples thereof include linear or branched C _1-10 alkyl groups such as a group, n-pentyl group, n-hexyl group, nonyl group, isononyl group and 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 a cyclopentyl group and a 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 not only fully unsaturated but also partially saturated. 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. A preferred aryl group is a C _6-10 aryl group such as a phenyl group or a naphthyl group.

The aralkyl group (arylalkyl group) represented by R ³ is a group in which the aryl group and the alkyl group are bonded. For example, benzyl group, phenethyl group, 3-phenyl-n-propyl group, 1-phenyl -N-hexyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-ethyl group, 1- (naphthalen-2-yl) -n-propyl group, inden-1-yl-methyl group, etc. Examples thereof include a C _6-12 aryl C _1-6 alkyl group. A preferred aralkyl group is a C _6-10 aryl C _1-4 alkyl group such as a benzyl group or a 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 a methoxy group, a C _1-6 alkoxy group such as ethoxy group. Examples of the acyl group include formyl group; C _1-10 alkyl-carbonyl group such as acetyl group and propionyl group. Examples of the alkoxycarbonyl group include C _1-4 alkoxy-carbonyl groups such as a methoxycarbonyl group. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group and an ethyl group.

Examples of the cyanoalkyl group represented by R ³ include cyano C _1-6 alkyl groups such as a cyanomethyl group and a cyanoethyl group. A preferable cyanoalkyl group is a cyano C _1-4 alkyl group, more preferably a cyano C _1-2 alkyl group, and particularly preferably 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, etc., and the carbon atom of the triazine ring May be substituted with an amino group, a hydroxyl group, or the like. Representative triazine-alkyl groups include, for example, 4,6-diamino-1,3,5-triazin-2-yl-methyl group, 4-amino-6-hydroxy-1,3,5-triazine-2 Examples include 1,3,5-triazin-2-yl-C _1-4 alkyl groups such as -yl-methyl group and 4,6-dihydroxy-1,3,5-triazin-2-yl-methyl group. . A preferred triazine-alkyl group is a 4,6-diamino-1,3,5-triazin-2-yl-C _1-2 alkyl group.

When R ³ and R ⁴ do not form a ring, preferred R ³ includes a hydrogen atom, a C _1-4 alkyl group, a C _6-10 aryl group, a C _6-10 aryl C _1-4 alkyl group, a cyano C _{It is a 1-3} alkyl group or a 1,3,5-triazin-2-yl-C _1-2 alkyl group, and is usually a hydrogen atom, a cyanoethyl group or the like in many cases.

The halogen atom represented by R ^{4 to} R ⁶ includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group 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. As the preferable alkyl group, hereinafter, stepwise linear or branched C _1-18 alkyl group, linear or branched C _1-12 alkyl group, linear or branched C _{1 1- A 10} alkyl group, a linear or branched C _1-6 alkyl group, and a linear or branched C _1-4 alkyl group.

^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 hydroxy C _1-20 alkyl groups such as hydroxymethyl group and hydroxyethyl group. Preferable hydroxyalkyl groups are shown below in a stepwise manner: hydroxy C _1-18 alkyl group, hydroxy C _1-16 alkyl group, hydroxy C _1-12 alkyl group, hydroxy C _1-8 alkyl group, hydroxy C _1-6 An alkyl group and a hydroxy _C1-4 alkyl group, more preferably a hydroxy _C1-2 alkyl group, and most preferably a hydroxymethyl group.

Examples of the cycloalkyl group, aryl group, and aralkyl group represented by R ^{4 to} R ⁶ include the same groups including the substituent R ³ and preferred embodiments.

The acyl group represented by R ^{4 to} R ⁶ may be a group in which a hydrogen atom; or 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 optionally substituted alkenyl-carbonyl group, an alkynyl-carbonyl group, an aryl-carbonyl group, and a heteroaryl-carbonyl group. Examples include groups.

Examples of the linear or branched alkyl-carbonyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, and 3-methylnonanoyl group. 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, Icosanoyl group, f Linear or branched C _1-26 alkyl such icosanoyl group -, carbonyl groups and the like.

Examples of the optionally substituted alkenyl-carbonyl group include an optionally substituted C _2-6 alkenyl-carbonyl group such as an acryloyl group, a methacryloyl group, an allylcarbonyl group, and a cinnamoyl group. Etc. Examples of the substituent include an aryl group.

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

Examples of the aryl-carbonyl group include C _6-18 aryl-carbonyl groups such as a benzoyl group, a naphthylcarbonyl group, a biphenylcarbonyl group, and an anthranylcarbonyl 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.

A preferable acyl group is a linear or branched C _1-20 alkyl-carbonyl group, and more preferably a linear or branched C _1-6 alkyl-carbonyl group.

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 a range of, for example, about 4 to 12 membered ring, and is preferably a 5 to 10 membered ring.

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

The double line between the solid line and the broken line represents a single bond or a double bond. Usually, when R ³ and R ⁴ are bonded to each other to form a ring (heterocycle), it may be a single bond, ^{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 examples of R ⁵ and / or R ⁶ include a hydrogen atom, an alkyl group, and a hydroxyalkyl group.

  More specifically, examples of the heterocyclic compound (guest compound) represented by the formula (2) include a compound represented by the following formula (2a) and / or a compound represented by the following formula (2b). Can be mentioned.

(In the formula, q represents an integer of 0 to 5; R ^{3 to} R ⁶ and a double line of a solid line and a broken line are the same as those in the formula (2) including a preferred embodiment).

In the formula (2a), more preferable embodiments of R ³ include a hydrogen atom, a cyanoethyl group, and a triazine-alkyl group, and more preferably a hydrogen atom.

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

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

In the formula (2a), the type of bond between the carbon atoms to which R ⁵ and R ⁶ are bonded may be a single bond (imidazoline compound). A bond (imidazole compound) is preferred.

  In the formula (2b), the preferable number of repetitions q is an integer of 1 to 5, more preferably an integer of 1 to 4, 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. Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

  Examples of the imidazole compound include imidazole; 1-alkylimidazole such as 1-methylimidazole, 1-ethylimidazole, 1-n-propylimidazole, 1-isopropylimidazole, 1-n-butylimidazole, 1-isobutylimidazole; 2 2-alkylimidazoles such as methylimidazole, 2-ethylimidazole, 2-n-propylimidazole, 2-isopropylimidazole, 2-n-butylimidazole, 2-isobutylimidazole, 2-undecylimidazole, 2-heptadecylimidazole 2-arylimidazoles such as 2-phenylimidazole; 4-alkylimidazoles such as 4-methylimidazole and 4-ethylimidazole; 1 such as 1,2-dimethylimidazole; 2-dialkylimidazole; 2,4-dialkylimidazole such as 2,4-dimethylimidazole and 2-ethyl-4-methylimidazole; 2-aryl-4-alkylimidazole such as 2-phenyl-4-methylimidazole; 1-aralkyl-2-alkylimidazole such as benzyl-2-methylimidazole; 1-aralkyl-2-arylimidazole such as 1-benzyl-2-phenylimidazole; 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2 1-cyanoethyl-2-alkylimidazole such as undecylimidazole; 1-cyanoethyl-2-arylimidazole such as 1-cyanoethyl-2-phenylimidazole; 1-cyanoethyl-2-ethyl-4-methylimidazole 1-cyanoethyl-2,4-dialkylimidazole; 2-aryl-4-alkyl-5-hydroxyalkylimidazole such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; 2-phenyl-4,5-bis And 2-aryl-4,5-bis (hydroxyalkyl) imidazole such as (hydroxymethyl) imidazole.

In many cases, at least one of R ^{3 to} R ⁶ is a substituent other than a hydrogen atom in the imidazole compound, and preferably at least one of R ^{3 to} R ⁵ is a substituent other than a hydrogen atom. More preferably, at least one of R ^{4 and} R ⁵ is a substituent other than a hydrogen atom, and among them, at least R ⁴ is preferably a substituent other than a hydrogen atom.

  As the compound represented by the formula (2b) (bicyclic amidine compound), for example, diazabicycloundecene (DBU: 1,8-diazabicyclo [5.4.0] -7-undecene), And diazabicyclononene (DBN: 1,5-diazabicyclo [4.3.0] -5-nonene).

These heterocyclic compounds (guest compounds) can be used alone or in combination of two or more. Of these heterocyclic compounds, a compound represented by the formula (2a) is preferable, and an imidazole compound is particularly preferable. Preferable 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 _6-12 aryl-imidazole such as 2-phenylimidazole; 2,4-diC _1-6 alkyl-imidazole such as 2-ethyl-4-methylimidazole; 1-cyanoethyl- 1-cyanoethyl-2,4-diC _1-6 alkyl-imidazole such as 2-ethyl-4-methylimidazole.

Among these, in applications where rapid curability is important, 2-C _1-4 alkyl-imidazole such as 2-methylimidazole; 2,4-diC _1-4 alkyl- such as 2-ethyl-4-methylimidazole. Imidazole is preferred, more preferably 2-C _1-2 alkyl-imidazole and 2,4-diC _1-2 alkyl-imidazole, and particularly preferably 2-C _1-2 alkyl-imidazole. In applications where high storage stability is important, 2-C _6-10 aryl-imidazoles such as 2-phenylimidazole are preferred. Among these, 2-C _6-10 such as 2-phenylimidazole has an excellent balance between rapid curability 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, for example, organic acids such as trimellitic acid, pyromellitic acid, and isocyanuric acid, or inorganic acids such as hydrochloric acid.

  The guest compound is not necessarily required in addition to the guest compound (first guest compound) having a 5- or 6-membered heterocyclic ring containing a plurality of nitrogen atoms as a constituent atom of the ring described above or a condensed heterocyclic ring thereof. Other guest compounds (or second guest compounds) that do not belong to the category of the first guest compound may be included.

  The second guest compound is not particularly limited, and is a conventional amine compound such as aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines (provided that the first guest compound is And the like, and specifically, amine compounds exemplified as other curing agents and / or curing accelerators to be described later. These 2nd guest compounds can also be used individually or in combination of 2 or more types.

  The ratio of the first guest compound may be selected from a range of, for example, about 10% by mass or more, specifically about 30 to 100% by mass with respect to the entire guest compound included in the host compound. The preferable range is 50% by mass or more, 60% by mass or more, 70% by mass or more, and 80% by mass or more stepwise, and the more preferable range is 90% by mass or more, 95% by mass or more, particularly It is preferably 100% by mass (substantially only the first guest compound). In addition, when a 2nd guest compound is included, the said ratio may be 60-99 mass%, for example, Preferably it may be 80-95 mass%.

  The ratio of the guest compound represented by the formula (2a) and / or (2b) is, for example, about 10% by mass or more, specifically about 30 to 100% by mass with respect to the entire first guest compound. You may select from a range. The preferable range is 50% by mass or more, 60% by mass or more, 70% by mass or more, and 80% by mass or more stepwise, and the more preferable range is 90% by mass or more, 95% by mass or more, particularly 100% by mass (substantially only the guest compound represented by the formula (2a) and / or (2b)). In addition, when the 1st guest compound which does not belong to the category of the said Formula (2a) and / or (2b) is included, even if the said ratio is 60-99 mass%, Preferably it is 80-95 mass%, for example. Good.

  In the inclusion compound, the ratio of the guest compound to the mole of the host compound (or the inclusion ratio) can be selected, for example, from a range of about 0.5 to 10 moles. .8 to 8 mol, 1 to 5 mol, 1.5 to 4.5 mol, and more preferably 2 to 4 mol. In the present invention, since the inclusion ratio can be easily adjusted, 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, more preferably 3.5 to 4.5 moles.

  In the inclusion compound, the phenolic hydroxyl group may form a salt, for example, a salt with a base. In the present invention, the inclusion compound includes a compound that forms such a salt as long as it has an inclusion form.

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

  When at least one of the host compound and 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. In addition, as said mixing temperature, normal temperature or about 30-100 degreeC may be sufficient, for example, Preferably it is 50-100 degreeC, and it is usually 70-90 degreeC in many cases.

  Mixing of the host compound and guest compound may be performed in the presence of a solvent, if necessary. The solvent typically includes 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 methyl carbitol), diethylene glycol monoethyl ether (or ethyl carbitol), diethylene glycol monobutyl ether (Or butyl carbitol) and other carbitols, dioxane, tetrahydrofuran and other cyclic ethers, diethyl ether and other chain ethers Tells, etc .; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, chain ketones such as 2-pentanone and 2-hexanone, cyclic ketones such as isophorone and cyclohexanone, etc .; esters such as methyl acetate and acetic acid Acetic esters such as ethyl, propyl acetate, butyl acetate and isobutyl acetate; ether esters such as 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, octane, etc .; alicyclic hydrocarbons For example, cyclohexane and the like; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; amides such as amides such as dimethylformamide and dimethylacetamide; sulfoxides Examples thereof include dimethyl sulfoxide.

  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. Of these solvents, esters such as ethyl acetate are usually 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.

  You may perform mixing (or reaction), stirring as needed. The mixing (or reaction) may be performed under heating, and the mixing temperature (or heating temperature) is not higher than the boiling point of the solvent, for example, 30 to 120 ° C., preferably 50 to 100 ° C., usually 70 Often -90 ° C. When heated, it may be cooled as necessary to recover the generated solid. 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 using a solvent, after completion of the mixing (or reaction), the solvent may be distilled off by a conventional method such as atmospheric distillation or vacuum distillation, if necessary. Moreover, the mixture containing a solvent may precipitate the clathrate compound by mixing with a solvent different from the solvent used for mixing. The collected clathrate may be washed or dried as necessary. As a drying method, vacuum drying is preferable. As drying temperature, it is 50-100 degreeC, for example, Preferably it is 70-90 degreeC.

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

[Curable composition]
In the present invention, whether the host compound represented by the formula (1) stably includes a predetermined heterocyclic compound that functions as a curing agent and / or a curing accelerator of an epoxy resin (epoxy compound), or an epoxy resin. It is stable for a long time even at low temperatures (normal temperature or storage temperature). On the other hand, the inclusion compound can rapidly cure the epoxy resin when it is heated to a predetermined temperature in order to release the heterocyclic compound with heating. In addition, in the inclusion compound, the heterocyclic compound as the guest compound has a secondary amino group and / or a tertiary amino group, or functions as a curing agent for the epoxy resin and as a curing accelerator. It can also function. 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 is used in preparing a curable composition in combination with the epoxy resin (epoxy compound). Useful.

(Second curing agent and / or curing accelerator)
The curable composition of the present invention only needs to 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 epoxy resin curing agent and A curing accelerator (also referred to as a second curing agent and / or a curing accelerator) may be included. Such a curing agent is not particularly limited as long as it is a compound that reacts with the oxirane ring (or epoxy group) of the epoxy resin to cure the epoxy resin, and the curing accelerator is a compound that accelerates the curing reaction of the epoxy resin. If there is, there is no particular limitation. Examples of such curing agents and / or curing accelerators include amine compounds, amide compounds, ester compounds, phenol compounds, alcohol compounds, thiol compounds, ether compounds, thioether compounds, and urea 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 the amine compound 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, 2,5-dimethyl. -Linear or branched alkylene diamines such as 2,5-hexanediamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, pentamethyldiethylenetriamine; dimethylaminopropylamine; N, N-dialkylaminoalkylamines such as diethylaminopropylamine and dibutylaminopropylamine; bis (2-dimethylaminoethyl) ester (Poly) ether diamines such as ter, diethylene glycol bis (3-aminopropyl) ether, polypropylene glycol diamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl N-alkyl-substituted alkylenediamines such as hexamethylenediamine and N, N, N ′, N′-tetramethylpropylenediamine; alkanolamines such as dimethylaminoethoxyethoxyethanol, triethanolamine and dimethylaminohexanol; mono-t -Linear or branched alkylamines, such as alkylamine, etc. are mentioned.

  Examples of the 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 And cyclohexanediamine such as 1,4-cyclohexanediamine; hydrogenated m-xylylenediamine; hydrogenated 1,3,5-tris (aminomethyl) benzene, and the like.

  Aromatic amines include, for example, phenylenediamines such as o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine; mono to or from m-xylylenediamine, 1,3,5-tris (aminomethyl) benzene, and the like. Tri (aminomethyl) benzenes; mono to tri (dialkylaminomethyl) phenols such as 2- (dimethylaminomethyl) phenol and 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; phthalocyanines such as phthalocyanine tetramine Nin'amin like; benzyl methylamine, benzyl dimethylamine, (alpha-methylbenzyl) methylamine, and the like benzyl alkyl amines such as (alpha-methylbenzyl) ethylamine.

  Heterocyclic amines can be broadly 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 picoline; piperidines such as piperidine and 4-amino-2,2,6,6-tetramethylpiperidine; pyrrole, Examples include pyrroles such as 2H-pyrrole; morpholines such as morpholine, methylmorpholine, and ethylmorpholine.

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

  Examples of the modified amines include polyamines (or amine adducts) obtained by adding amines to epoxy compounds, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-capped polyamines (ketimines), dicyandiamide, guanidine, organic acid hydrazides, Examples include diaminomaleonitrile, amine imide, boron trifluoride-piperidine complex, and boron trifluoride-monoethylamine complex.

  These amine compounds may be salts with acids, for example, organic acids such as 2-ethylhexylic acid, trimellitic acid, pyromellitic acid, and isocyanuric acid, or inorganic acids such as hydrochloric acid.

  Examples of the amide 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 alkylene diamine and polyethylene polyamine.

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

  Examples of phenolic compounds include phenolic resin curing agents such as phenol aralkyl resins, aralkyl phenol resins such as naphthol aralkyl resins, novolac phenol resins such as phenol novolac resins and cresol novolac resins, and modified resins thereof such as Phenolic resins such as epoxidized or butylated novolac type phenolic resins; modified phenolic resins such as dicyclopentadiene modified phenolic resin, paraxylene modified phenolic resin, triphenolalkane type phenolic resin, polyfunctional phenolic resin, etc. It can be illustrated.

  Examples of alcohol compounds include polyols. Examples of the thiol compound include polymercaptan. Examples of ether compounds include polyethers. Examples of thioether compounds include polysulfides. Examples of urea compounds include butylated urea and butylated melamine. Examples of the thiourea compound include butylated thiourea. Examples of the Lewis acid compound include boron trifluoride.

  Examples of phosphorus compounds include organic phosphine compounds such as alkyl phosphines such as ethyl phosphine and butyl phosphine, and first phosphines such as aryl phosphines such as phenyl phosphine; dialkyl phosphines such as dimethyl phosphine, dipropyl phosphine, and methyl ethyl phosphine; Second phosphines such as diarylphosphine such as diphenylphosphine; trialkylphosphines such as trimethylphosphine and triethylphosphine, and third phosphines such as triarylphosphine such as triphenylphosphine.

  Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate). Aromatic hydrocarboxylic anhydrides such as: tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenic carboxylic anhydride, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, anhydrous hymic acid, anhydrous methyl hymic acid, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro (B) Alicyclic polycarboxylic anhydrides such as phthalic anhydride (methyl nadic anhydride); maleic anhydride, tetramethylene maleic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelinic anhydride, polysebacic anhydride , Aliphatic polycarboxylic acid anhydrides such as poly (ethyl octadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride; het acid anhydride (chlorendic acid anhydride), tetrabromophthalic anhydride, tetrachlorophthalic anhydride And halogenated acid anhydrides.

  Examples of the onium salt compounds include aryldiazonium salts, diaryliodonium salts, arylsulfonium salts, arylmethylsulfonium salts, diarylsulfonium salts, and triarylsulfonium salts. Arylmethylsulfonium salts and the like are often used, and examples thereof include benzylmethylsulfonium salts.

  Examples of the active silicon compound-aluminum complex include a triphenylsilanol-aluminum complex, a triphenylmethoxysilane-aluminum complex, a silyl peroxide-aluminum complex, and a triphenylsilanol-tris (salicylide) aluminum complex.

  These 2nd hardening | curing agents and / or hardening accelerators can be used individually or in combination of 2 or more types. The ratio of the inclusion 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. 30/70, preferably 100/0 to 50/50, more preferably 100/0 to 70/30, still more preferably 100/0 to 90/10, especially 100/0 (substantially only the inclusion compound) Is preferred.

  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 curing accelerator is based on the epoxy group in the epoxy resin. For example, 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, and a hydroxyl group.

(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, and the like. .

  Examples of the glycidyl ether type epoxy resin (or compound) include, for example, glycidyl ethers of alkane monools, polyglycidyl ethers of alkane polyols, mononuclear polyhydric phenols or polyglycidyl ethers of alkylene oxide adducts thereof, and polynuclear polyhydric polyvalents. Examples include polyglycidyl ethers of phenols or alkylene oxide adducts thereof, and polyglycidyl 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. Etc.

  In the polyglycidyl ether of alkane polyols, examples of the alkane polyols include ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiethylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol. Etc.

  In the polyglycidyl ether of mononuclear polyhydric phenols or alkylene oxide adducts thereof, examples of the mononuclear polyhydric phenols include hydroquinone, resorcin, pyrocatechol, and phloroglucinol.

  In the polyglycidyl ether of polynuclear polyhydric phenols or alkylene oxide adducts thereof, examples of polynuclear polyhydric phenols include dihydroxynaphthalene, biphenol, bisphenols, tris or tetrakis (hydroxyphenyl) alkane, novolac or novolac resin, Examples include terpene phenol.

  Examples of bisphenols include methylene bisphenol (or bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (or bisphenol AD), isopropylidene bisphenol (or bisphenol A), isopropylidene bis (orthocresol), and 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), 9,9-bis (hydroxyaryl) fluorene, and the like. 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, And 9-bis (5-hydroxy-1-naphthyl) fluorene.

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

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

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

  Examples of the polyglycidyl 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 glycidyl versatic acid ester; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, Aliphatic acids such as azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid And glycidyl esters of alicyclic or aromatic polycarboxylic acids; homopolymers or copolymers of glycidyl (meth) acrylate.

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

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

  These epoxy resins (or compounds) can be used alone or in combination of two or more. In addition, a monomer may be sufficient as an epoxy resin (or compound), and the multimer about a dimer-decamer may be included. Also, mono- or polyglycidyl ethers of alkane monools or alkane polyols, glycidyl esters of monocarboxylic acids, epoxidized products of cyclic olefins, etc. are often used as reactive diluents.

  Preferred epoxy resins include polyglycidyl ethers having a plurality of epoxy groups (or oxirane rings) in the molecule, such as methylene bisphenol (or bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (or bisphenol AD), isopropylidene. Examples thereof include bisphenols such as bisphenol (or bisphenol A), isopropylidenebis (orthocresol), and 9,9-bis (hydroxyaryl) fluorene, or polyglycidyl ethers of alkylene oxide adducts 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., a semi-solid or solid having high viscosity (or high viscosity) with poor fluidity. Ordinarily, it may be a liquid or viscous liquid epoxy resin that has fluidity at the temperature (mixing temperature or processing temperature) at which it is mixed with the clathrate compound and is liquid at the mixing temperature.

  In the curable composition of the present invention, the ratio of the inclusion compound can be appropriately selected according to 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, addition type curing in which a first guest compound or heterocyclic compound (first curing agent and / or curing accelerator) is necessarily incorporated into a cured resin by a covalent bond by reaction with an epoxy group in the epoxy resin. In the case of an agent, the ratio of the clathrate compound is usually 0.1 to 1 in terms of the clathrated heterocyclic compound with respect to 1 mol of the epoxy group (or oxirane ring) depending on the properties of the cured resin. It can select from the range of about a mole, Preferably it is 0.2-0.8 mol, More preferably, it is 0.25-0.5 mol.

  In addition, the heterocyclic compound is not incorporated into the cured resin by a covalent bond, but it induces the ring opening of the epoxy group catalytically and causes a polymerization addition reaction between the epoxy compounds. In the case of being an agent or when used as a curing accelerator, the ratio of the clathrate compound is about 1 mol or less in terms of the clathrated heterocyclic compound with respect to 1 mol of the epoxy group (or oxirane ring). The range is preferably 0.001 to 0.5 mol, and 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, for example, 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 preferably 1.5 to 5 parts by mass.

  The curable composition of this invention can be manufactured by mixing the hardening | curing agent and / or hardening accelerator component containing the said clathrate compound, and 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, a roll, an extruder, or the like, a raking machine (crusher) Or the like, and may be prepared by mixing or kneading at a temperature and time at which the curing reaction (or gelation) does not occur or can be suppressed. The kneading may be, for example, melt kneading.

  Mixing or kneading may be performed under heating, for example, at about 50 to 100 ° C., but mixing at low temperature, for example, about 0 to 50 ° C., preferably mixing or kneading in an ice bath, and mixing under heating. Or, kneading is often omitted. In addition, you may mix or knead | mix in presence of the solvent illustrated to the term of the manufacturing method of the said clathrate compound.

  In the curable composition of the present invention, various additives, for example, silane coupling agents, plasticizers, organic solvents, reactive diluents, fillers, reinforcing agents, colorants such as pigments, and the like as necessary. Stabilizers such as flame retardants, mold release agents, antioxidants, ultraviolet absorbers, extenders, thickeners and the like may be added.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3 -(Meth) 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-mercapto Etc. b pills triethoxy silane.

  Examples of the plasticizer include alkane dicarboxylic acid plasticizers such as phthalic acid plasticizers and adipic acid plasticizers, phosphate ester plasticizers, and polyester plasticizers.

  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 epoxy compounds exemplified above, for example, epoxy compounds such as n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl ether, dicyclopentadiene diepoxide, phenol, cresol, t -Phenols such as butylphenol.

  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; Examples thereof include metal borates such as aluminum borate; metal titanates such as potassium titanate; minerals such as talc, kaolin, clay, mica, wollastonite, sepiolite, and zonotlite. Examples of calcium carbonate include calcium bicarbonate and light calcium carbonate. Examples of silica include natural silica, synthetic silica, and fused silica.

  The reinforcing agent can be roughly classified into, for example, organic fibers and inorganic fibers. Examples of organic fibers include natural fibers such as cellulose fibers and cellulose nanofibers; and synthetic fibers such as polyalkylene arylate 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, and green pigments.

  Examples of the flame retardant include hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyl oxide, bis (pentabromo) phenylethane. , Tris (tribromophenoxy) triazine, ethylenebistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, brominated compounds such as polypentabromobenzyl acrylate, triphenyl phosphate, tri Cresyl phosphate, trixinyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate, Zirbis (di-2,6-xylenyl) phosphate, 2-ethylhexyl diphenyl 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, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, etc. Phosphate esters, anion oxalic acid treated aluminum hydroxide, nitrate treated aluminum hydroxide, high temperature hot water treated aluminum hydroxide, stannic acid surface treated hydrated metal compound , Surface treated magnesium hydroxide a nickel compound, a silicone polymer surface treatment of magnesium hydroxide, procolipase bytes, multilayer surface-treated hydrated metal compound, and a cationic polymer treatment magnesium hydroxide.

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

  Furthermore, 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 ( Core-shell acrylic rubber), urethane rubber, polyester elastomer, functional group-containing liquid NBR, liquid polyester, liquid polysulfide, urethane prepolymer, and the like.

  Moreover, the curable composition may contain other resin (or 2nd resin) other than an epoxy resin if necessary. Examples of the second resin include olefin resins such as high density polyethylene and polypropylene, styrene resins such as polystyrene, acrylic resins such as polymethyl methacrylate, halogen-containing resins such as polyvinyl chloride, and polyethylene terephthalate. 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, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetheretherketone.

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

  The present invention also includes a cured product obtained by curing the curable composition. Such hardened | cured material can be prepared by heating and hardening the said curable composition according to the use of a curable composition. For example, the curable composition may be applied to a substrate and cured, injected or sealed into a predetermined part, cured, cast and cured, fiber substrate, etc. A prepreg may be prepared by impregnating the base material, and the prepreg may be laminated by a method such as superposition or winding, molded 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. In addition, since the curable composition of the present invention can be quickly cured even at a relatively low temperature, the preferable heating temperature is 100 to 160 ° C, more preferably 120 to 150 ° C, and most preferably 130 to 140 ° C. It 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 a preferable range is 25 minutes or less and 20 minutes or less step by step. 15 minutes or less, and more preferably 10 minutes or less. The gelation time is, for example, 0.1 to 15 minutes, preferably 1 to 10 minutes.

  The curable composition of the present invention has unexpectedly high storage stability (or storage stability) despite being able to cure quickly at low temperatures. Therefore, after the preparation of the curable composition, the viscosity at 25 ° C. after being stored sealed at 25 ° C. for 24 hours is the initial viscosity at 25 ° C. immediately after the preparation of the curable composition (after 0 hours of preparation), for example, The preferred 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 below, and 1.3 times or less is the most preferable.

  In addition, in this specification and a claim, the said gelation time and a viscosity can be measured by the method as described in the Example mentioned 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 H-NMR)
¹ H-NMR was measured by dissolving an inclusion compound in deuterated chloroform, deuterated methanol, deuterated dimethyl sulfoxide and the like and 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. Preparation of inclusion compound [Example 1] (Synthesis of inclusion compound of BINOL: 2E4MZ)
To a solution of 1,1′-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) in ethyl acetate (100 g) at 80 ° C., 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industries, Ltd.) , 13.2 g, 120 mmol) in ethyl acetate (50 g) was added. After stirring for 1 hour, the heating was stopped, and after cooling to 10 ° C., the resulting solid was collected by filtration and dried to give the product (white solid, yield 23.6 g). 6, 11 and 20 show the measurement results of ¹ H-NMR, XRD and TGA of the resulting clathrate compound. XRD confirmed that the compound was a crystalline compound different from BINOL alone. Moreover, it was confirmed by ¹ H-NMR that the obtained inclusion compound was an inclusion compound having an inclusion ratio of BINOL: 2E4MZ = 1: 2. Further, 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, two broken lines drawn parallel to the horizontal axis (temperature) indicate the start of measurement and the completion of guest release, and “ΔY” The mass ratio of the guest compound in the contact compound is shown (hereinafter the same).

[Example 2] (BINOL: Synthesis of inclusion compound of 2MZ-H)
1,1′-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) and 2-methylimidazole (2MZ-H, manufactured by Shikoku Chemicals Co., Ltd., 9.9 g, 120 mmol) and ethyl acetate (50 g) Was dissolved at 80 ° C. After stirring for 1 hour, the heating was stopped, and after cooling to 10 ° C., the resulting solid was collected by filtration and dried to obtain the product (white solid, yield 16.7 g). The measurement results of ¹ H-NMR, XRD and TGA of the clathrate compounds obtained are shown in FIGS. XRD confirmed that the compound was a crystalline compound different from BINOL alone. Moreover, it was confirmed by ¹ H-NMR that the obtained inclusion compound was an inclusion compound having an inclusion ratio BINOL: 2MZ-H = 1: 2. Further, 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. Each is shown.

[Example 3] (BINOL: Synthesis of inclusion compound of 2E4MZ-CN)
1,1′-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) to 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN, manufactured by Shikoku Kasei Co., Ltd., 19.6 g, 120 mmol) ) And ethyl acetate (150 g) were added and dissolved by stirring at 80 ° C. for 1 hour. After stirring, the heating was stopped, and after cooling to 10 ° C., the resulting solid was collected by filtration and dried to obtain the product (white solid, yield 26.0 g). 8, 13 and 22 show the measurement results of ¹ H-NMR, XRD and TGA of the clathrate compound obtained. XRD confirmed that the compound was a crystalline compound different from BINOL alone. Moreover, it was confirmed by ¹ H-NMR that the obtained inclusion compound was an inclusion compound having an inclusion ratio BINOL: 2E4MZ-CN = 1: 2. Further, 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. Each is shown.

[Example 4] (BINOL: Synthesis of inclusion compound of 2PZ-PW)
1,1′-bi-2-naphthol (BINOL, 14.3 g, 50 mmol) and 2-phenylimidazole (2PZ-PW, manufactured by Shikoku Kasei Co., Ltd., 17.3 g, 120 mmol) and ethyl acetate (475 g) Was dissolved at 80 ° C. After stirring for 15 minutes, the heating was stopped, and after cooling to 10 ° C., the resulting solid was collected by filtration and dried to obtain the product (white solid, yield 12.0 g). The obtained inclusion compound shows the measurement result of ¹ H-NMR, XRD, and TGA of the inclusion compound obtained in FIGS. It was confirmed by XRD that the compound was a crystalline compound different from BINOL alone. Moreover, it was confirmed by ¹ H-NMR that the obtained inclusion compound was an inclusion compound having an inclusion ratio of BINOL: 2PZ-PW = 1: 4. Further, 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. Each is shown.

  Table 1 below shows the composition of each clathrate compound.

2. Preparation and test of curable composition [Example 5]
6.9 parts by mass of BINOL: 2E4MZ (3 parts by mass as 2E4MZ) was added to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and a homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd., Ace Homogenizer AM). -10), the mixture was stirred in an ice bath at a rotational speed of 15000 rpm for 15 minutes to prepare a curable composition.

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

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

[Comparative Example 1]
3 parts by mass of 2E4MZ is added to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and ice is produced at a rotational speed of 15000 rpm with a homogenizer (manufactured by Nippon Seiki Seisakusho, ACE homogenizer AM-10). The mixture was stirred for 15 minutes in a bath to prepare a curable composition.

[Comparative Example 2]
3 parts by mass of 2PZ-PW is added to 100 parts by mass of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation), and the number of revolutions is 15000 rpm with a homogenizer (manufactured by Nippon Seiki Seisakusho, ACE homogenizer AM-10). The mixture was stirred for 15 minutes in an ice bath to prepare a curable composition.

[Measurement of gelation time]
A glass sample tube and an aluminum block with a hole having 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) into the sample tube, insert the sample tube into the hole in the aluminum block, and stir the sample tube in a circle (like drawing a circle) at a speed of about 60 times per minute with a spatula The time point from the insertion of the sample tube to the end point was measured with the point where the sample became a gel and no longer adhered to the spatula or the point where the stringing disappeared. The results are shown in Table 2 below.

[Storage stability test of curable composition]
Using the E-type viscometer ("TVE-22L" manufactured by Toki Sangyo Co., Ltd.), the initial viscosity (viscosity at 25 ° C measured at 0 hours after preparation, mPa · s / 25 ° C) of the prepared curable composition was used. Measured. Subsequently, the produced curable composition was preserve | saved at 25 degreeC in the airtight container, and the viscosity after 24 hours preservation | save was measured similarly. 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 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 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 a 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 the epoxy resin is applied, for example, insulating materials, sealing materials, epoxy resin laminates, composite materials, casting materials, repair materials for concrete structures, adhesion It can be used for applications such as adhesives and coating agents.

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

Claims (10)

A curable composition comprising an epoxy resin and a clathrate compound as a curing agent and / or a curing accelerator, wherein the clathrate compound is represented by the following formula (1):

(Wherein R ¹ and R ² are each independently a substituent, m is each independently an integer of 0 to 4, and n is each independently an integer of 0 to 2).
And a guest compound having a 5- or 6-membered heterocyclic ring containing a plurality of nitrogen atoms as ring constituent atoms or a condensed heterocyclic ring thereof. In the 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, a halogen atom. The curable composition according to claim 1, wherein nitro group, cyano group or substituted amino group, m is an integer of 0 to 2, and n is 0 or 1. The guest compound is 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 represent a hydrogen atom, a halogen atom, or a nitro group. 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; and R ³ and R ⁴ are bonded to each other to form an adjacent nitrogen atom and A ring may be formed with a carbon atom; p represents an integer of 0 to 3; a double line between a solid line and a broken line represents a single bond or a double bond.)
The curable composition of Claim 1 or 2 containing the compound represented by these. The guest compound is represented by the following formula (2a) and / or (2b)

(In the formula, q represents an integer of 0 to 5; R ^{3 to} R ⁶ and a double line of a solid line and a broken line are the same as in claim 3).
The curable composition in any one of Claims 1-3 containing the compound represented by these.   The guest compound comprises at least one imidazole compound selected from 2-alkylimidazole, 2-arylimidazole, 2,4-dialkylimidazole and 1-cyanoethyl-2,4-dialkylimidazole. A curable composition according to any one of the above.   The curable composition according to any one of claims 1 to 5, wherein the clathrate compound contains the guest compound in a proportion of 0.5 to 5 mol with respect to 1 mol of the host compound.   The curable composition according to any one of claims 1 to 6, wherein the epoxy resin is a liquid epoxy resin.   The curable composition in any one of Claims 1-7 which contain the guest compound in a clathrate compound in the ratio of 0.1-25 mass parts with respect to 100 mass parts of epoxy resins.   An inclusion compound comprising a host compound represented by the formula (1) according to claim 1 and a guest compound having a 5- or 6-membered heterocyclic ring containing a plurality of nitrogen atoms as ring constituent atoms or a condensed heterocyclic ring thereof. A method for producing a curable composition according to claim 1, mixed with an epoxy resin.   Hardened | cured material which the curable composition in any one of Claims 1-8 hardened | cured.

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