KR20190039165A - INCLUSION COMPOUND AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

(식 중, Ar¹, Ar², Z¹ 및 Z²는 단환식 또는 축합 다환식 아렌환을 나타내고; R¹, R², R³ 및 R⁴는 치환기를 나타내고; n1 및 n2는 0 내지 4의 정수를 나타내고, n1 및 n2 중 적어도 한쪽이 1 이상의 정수이고; m1, m2, p1 및 p2는 각각 동일하거나 또는 상이하며 0 내지 4의 정수를 나타내고;
R⁵는 수소 원자, 알킬기, 시아노에틸기, 트리아진-알킬기 등을 나타내고, R⁶ 내지 R⁸은 수소 원자, 알킬기, 아릴기 등을 나타내고, R⁵와 R⁶은 서로 결합하여 환을 형성해도 되고; q는 0 또는 1 내지 3의 정수를 나타내고; 실선과 파선의 이중선은 단결합 또는 이중 결합을 나타낸다)The inclusion compound of the present invention is a compound represented by the formula (1) wherein a compound having a 9,9-bisarylfluorene skeleton having a phenolic hydroxyl group is hosted and represented by the formula (2) A 5 or 6 membered heterocycle containing an atom or a compound having a condensed heterocycle thereof as a guest. The inclusion compound is useful as a curing agent and / or a curing accelerator of an epoxy resin.

^{(Wherein, Ar 1, Ar 2, Z} 1 and Z ² denotes a monocyclic or condensed polycyclic arene ^{ring; R 1, R 2, R} 3 and R ⁴ represents a substituent; n1 and n2 is from 0 to 4 At least one of n1 and n2 is an integer of 1 or more; m1, m2, p1 and p2 are the same or different and each represents an integer of 0 to 4;
R ⁵ represents a hydrogen atom, an alkyl group, a cyano group, a triazine-alkyl group or the like, R ⁶ to R ^{8 each} represent a hydrogen atom, an alkyl group, an aryl group or the like, and R ⁵ and R ⁶ , Being; q represents 0 or an integer of 1 to 3; And the double line of the solid line and the broken line represents a single bond or a double bond)

Description

INCLUSION COMPOUND AND METHOD FOR PRODUCING THE SAME

The present invention relates to a novel inclusion compound having a fluorene compound as a host, a process for producing the same, and a use thereof (a curing agent and / or a curing accelerator, a curing composition and a cured product thereof).

The 9,9-bisarylfluorene compound is used as a raw material for electronic materials and optical materials because of its excellent heat resistance and excellent optical properties (transparency, refractive index, etc.). For example, JP-A-2013-203695 (Patent Document 1) discloses that an epoxy compound having a 9,9-bisarylfluorene skeleton and a triazine skeleton has high heat resistance and solubility in an organic solvent Japanese Patent Laid-Open Publication No. 2013-64119 (Patent Document 2) discloses a polyester resin comprising a specific diol component having a fluorene skeleton and a dicarboxylic acid component having a fluorene skeleton as a polymerization component, And has a refractive index and a low refractive index.

The 9,9-bisarylfluorene compound has a function of covering the small molecule derived from the volume size of the molecular structure in addition to the above-mentioned characteristic. For example, Japanese Patent Application Laid-Open No. 2009-234998 (Patent Document 3) discloses a process for producing a compound represented by Formula (1), wherein a 9,9-bisarylfluorene compound is used as a host compound and an alcohol, an ether, a ketone, an ester, In the examples of this document, it is described that an inclusion compound containing a bisphenol A or a hydroxycarboxylic acid or a hydrocarbons as a guest compound is used. In the examples of this document, biscresol fluorene is reacted with bisphenol A, dihydric alcohols such as 1-adamantanol, acetic acid diacetate, acetone, isopropanol, And inclusion compounds such as ether are described. Japanese Patent Application Laid-Open No. 6-166646 (Patent Document 4) discloses a process for producing an alkoxysilane compound by reacting an alkane tetrakisphenol such as 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) And examples of the guest compound include monocyclic nitrogen-containing heterocyclic compounds such as pyridine and imidazole in addition to alcohols. In the examples, diethylamine, triethylamine, and the like are used as guest compounds An example used is described. Japanese Patent Application Laid-Open No. 11-71449 (Patent Document 5) discloses a process for preparing a compound represented by the formula (1) in which an alkane tetrakisphenol such as 1,1,2,2-tetrakis (4-hydroxyphenyl) It has been proposed to use an inclusion compound as a guest compound as a curing agent or curing accelerator of an epoxy resin.

Such an inclusion compound can improve the handling property by pulverizing the guest compound by increasing the chemical stability together with the nonvaporization of the guest compound. Further, it can be used in a wide range of fields such as a temperature-sensitive material using a material having a temperature dependence of release of a guest compound, and a separating material using selective separability. However, since the guest compound is limited, the use of the inclusion compound is limited.

Japanese Patent Application Laid-Open No. 2013-203695 (Claims, Examples) Japanese Patent Application Laid-Open No. 2013-64119 (Claims, Examples) Japanese Patent Application Laid-Open No. 2009-234998 (claims, examples) Japanese Patent Application Laid-Open No. 6-166646 (claims, embodiments, and the like) Japanese Patent Application Laid-Open No. 11-71449 (Claims, Examples)

Accordingly, an object of the present invention is to provide a novel inclusion compound containing a fluorene compound as a host, a process for producing the same, and a use thereof.

Another object of the present invention is to provide an inclusion compound useful as a curing agent and / or a curing accelerator for an epoxy resin, a process for producing the same, and a use thereof.

It is still another object of the present invention to provide a curable composition and a cured product thereof which have high storage stability without lowering the physical properties of the cured product and can be quickly cured by heating.

DISCLOSURE OF THE INVENTION As a result of intensive studies to achieve the above object, the present inventors have found that a compound having a 9,9-bisarylfluorene skeleton having a phenolic hydroxyl group forms an inclusion compound with a heterocyclic compound having a plurality of nitrogen atoms And that the use of this inclusion compound as a curing agent for an epoxy resin enables high storage stability and curing of the epoxy resin quickly by heating, thereby completing the present invention.

That is, the inclusion compound of the present invention can be produced by reacting a compound represented by the following formula (1) as a host compound and a 5 or 6 membered heterocyclic ring containing a plurality of nitrogen atoms (e.g., basic nitrogen atom) (For example, an aliphatic or aromatic heterocycle) or a compound having a condensed heterocycle thereof as a guest compound.

^{(Wherein, Ar 1, Ar 2, Z} 1 and Z ² are each the same or different and each represents a monocyclic arene ring or polycyclic arene ^{ring; R 1, R 2, R} 3 and R ⁴ are the same or each or M1, m2, p1 and p2 are the same or different from each other, and n1 and n2 are the same or different and each represent an integer of 0 to 4, at least one of n1 and n2 is an integer of at least 1, An integer of 0 to 4)

In the formula (1), the rings Ar ¹ and Ar ² are the same or different and each is a benzene ring or a naphthalene ring; Rings Z ¹ and Z ² are the same or different and are a benzene ring or a naphthalene ring; R ¹ and R ² are the same or different and are a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen An atom, a nitro group, a cyano group or a substituted amino group; R ³ and R ⁴ are the same or different and are a hydrocarbon group (an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group), an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group; n1 and n2 are the same or different and are an integer of 1 to 3; m1 and m2 are the same or different and are an integer of 0 to 2; p1 and p2 may be the same or different and may be an integer of 0 to 2.

The host compound is a compound wherein, in the formula (1), the rings Ar ¹ and Ar ² are benzene rings; Rings Z ¹ and Z ² are benzene rings or naphthalene rings; n1 and n2 are 1 or 2; R ¹ and R ² are the same or different and each is a C _1-4 alkyl group or a C _6-10 aryl group, m 1 and m 2 are integers of 0 to 2; In many cases, p1 and p2 are 0, and in formula (1), R ¹ and R ² are methyl groups or phenyl groups, and m1 and m2 are often 1 or 2.

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

(Wherein R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyano group or a triazine-alkyl group; R ⁶ to R ^{8 each} represent a hydrogen atom, a halogen atom, a nitro group, An alkyl group, an aryl group, an aralkyl group or an acyl group, the alkyl group may have a hydroxyl group, R ⁵ and R ⁶ may combine with each other to form a ring together with the adjacent nitrogen atom and carbon atom, q is 0 Or an integer of 1 to 3; and the double line of the solid line and the broken line represents a single bond or a double bond)

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

(In the formula, r represents an integer of 0 to 5; R ⁵ to R ⁸ and the double line of the solid line and the broken line are the same as above)

In the inclusion compound, the ratio of the guest compound may be about 0.5 to 5 moles relative to 1 mole of the host compound.

The inclusion compound can be produced by reacting a compound represented by the formula (1) with a 5 or 6-membered heterocycle (such as an aliphatic or aromatic heterocycle) containing plural nitrogen atoms (basic nitrogen atom, etc.) Can be prepared by mixing a compound having a heterocycle.

Since the heterocyclic compound contained in such an inclusion compound has a secondary amino group or a tertiary amino group, it can function as a curing agent or a curing accelerator for curing the epoxy resin. Therefore, the present invention relates to a curing agent or a curing accelerator containing the inclusion compound; Also included are curable compositions comprising the inclusion compound and an epoxy resin. In this curable composition, the epoxy resin may be a liquid epoxy resin. The amount of the inclusion compound may be about 0.1 to 25 parts by weight based on 100 parts by weight of the epoxy resin. The curable composition may further comprise at least one compound selected from a phenol compound and an acid anhydride compound (second curing agent).

The present invention relates to a cured product in which the curable composition is cured; And then curing the curable composition (for example, curing by heating) to produce a cured product.

In the present specification, a compound having a 5-membered or 6-membered heterocycle containing a plurality of nitrogen atoms or a condensed heterocycle thereof may be simply referred to as a "heterocyclic compound". Also, as described above, the heterocyclic compound has a secondary amino group or a tertiary amino group and can function as a curing agent or a curing accelerator for curing the epoxy resin. Therefore, there is a case where "curing agent or curing accelerator" is simply described as "curing agent". The "inclusion compound" is not limited to an inclusion compound of the compound represented by the formula (1) and the heterocyclic compound described above. The inclusion compound is not limited to the salinity formed by the phenolic hydroxyl group of the compound represented by the formula (1) Used in the sense that it includes.

In the present invention, a heterocyclic compound having a plurality of nitrogen atoms in a space formed by a fluorene compound having a 9,9-bisarylfluorene skeleton can be introduced as a guest compound, and a novel inclusion compound can be provided. This inclusion compound is useful as a curing agent or the like for an epoxy resin. In addition, the inclusion compound has high storage stability without lowering the physical properties of the cured product in the epoxy resin composition, and can be cured quickly by heating.

1 is a ¹ H-NMR spectrum of the inclusion compound of Example 1. Fig.
2 is a TG-DTA chart of the inclusion compound of Example 1, in which the solid line indicates TG and the broken line indicates DTA.
3 is a ¹ H-NMR spectrum of the inclusion compound of Example 2. Fig.
4 is a TG-DTA chart of the inclusion compound of Example 2, in which the solid line indicates TG and the broken line indicates DTA.
5 is a ¹ H-NMR spectrum of the inclusion compound of Example 3. Fig.
6 is a TG-DTA chart of the inclusion compound of Example 3, in which the solid line indicates TG and the broken line indicates DTA.
7 is a ¹ H-NMR spectrum of the inclusion compound of Example 4. Fig.
FIG. 8 is a TG-DTA chart of the inclusion compound of Example 4, in which the solid line indicates TG and the broken line indicates DTA.
9 is a ¹ H-NMR spectrum of the inclusion compound of Example 5. Fig.
10 is a TG-DTA chart of the inclusion compound of Example 5, in which the solid line indicates TG and the broken line indicates DTA.
11 is a ¹ H-NMR spectrum of the inclusion compound of Example 6. Fig.
12 is a TG-DTA chart of the inclusion compound of Example 6, in which the solid line indicates TG and the broken line indicates DTA.
13 is a DSC chart of the curable composition of Example 7. Fig.
14 is a DSC chart of the curable composition of Example 8. Fig.
15 is a DSC chart of the curable composition of Example 9. Fig.
16 is a DSC chart of the curable composition of Comparative Example 1. Fig.

(Inclusion compound)

In the inclusion compound, a small molecule is introduced as a guest in the space formed by the host molecule, and the guest stably exists regardless of the covalent bond.

(Host compound)

In the inclusion compound of the present invention, the host compound includes a compound represented by the formula (1).

^{(Wherein, Ar 1, Ar 2, Z} 1 and Z ² are each the same or different and each represents a monocyclic arene ring or polycyclic arene ^{ring; R 1, R 2, R} 3 and R ⁴ are the same or each or M1, m2, p1 and p2 are the same or different from each other, and n1 and n2 are the same or different and each represent an integer of 0 to 4, at least one of n1 and n2 is an integer of at least 1, An integer of 0 to 4)

Examples of the monocyclic arene ring (monocyclic aromatic hydrocarbon ring) represented by the rings Ar ¹ and Ar ² in the above formula (1) include benzene rings and the like. Examples of the polycyclic arene ring include condensed polycyclic alicyclic rings (condensed polycyclic hydrocarbon rings). Examples of the condensed polycyclic alicyclic ring include condensed bicyclic arenes (for example, condensed bicyclic C ₁₀ such as naphthalene) _-16 arylene) ring, condensed tricyclic arene (for example, anthracene, phenanthrene, etc.) ring, and the like. Preferable condensed polycyclic arene rings are naphthalene rings, anthracene rings and the like, in particular naphthalene rings.

Preferred rings Ar ¹ and Ar ² are benzene rings or naphthalene rings (for example, benzene rings). The rings Ar ¹ and Ar ² may be the same or different. For example, both of the rings Ar ¹ and Ar ² may be a benzene ring or a naphthalene ring, the ring Ar ¹ may be a benzene ring, and the ring Ar ² may be a naphthalene ring. The compound wherein the ring Ar ¹ is a benzene ring and the ring Ar ² is a naphthalene ring may form a benz [a] fluorene compound, a benz [b] fluorene compound or a benz [c] fluorene compound.

Examples of the monocyclic arene ring represented by rings Z ¹ and Z ² include a benzene ring and the like. The polycyclic arene rings include condensed polycyclic arene rings (condensed polycyclic hydrocarbon rings), ring condensed areylene rings (ring-substituted aromatic hydrocarbon rings), and the like. Examples of the condensed polycyclic arene ring include the same condensed areylene rings as the rings Ar ¹ and Ar ² , for example, a naphthalene ring, an anthracene ring and the like. A preferred condensed polycyclic arene ring is a naphthalene ring. Preferable rings Z ¹ and Z ² are benzene rings or naphthalene rings, and usually benzene rings.

Examples of the ring-set arene ring (ring-formed aromatic hydrocarbon ring ring) include a non-aromatic ring such as a bivalent ring such as a biphenyl ring, a binaphthyl ring, a phenyl naphthalene ring (1-phenylnaphthalene ring, _6-12 arene rings, terarylene rings, ter-C _6-12 arene rings such as terphenylen rings, and the like. Preferable ring-substituted arene rings include non-C _6-10 arene rings, particularly biphenyl rings.

The kinds of the substituents R ¹ , R ² , R ³ and R ⁴ are not particularly limited as long as they do not impair the folding of the guest compound, and examples thereof include halogen atoms, nitro groups, cyano groups, hydrocarbon groups (alkyl groups, cycloalkyl groups, an aralkyl group, etc.), a group -OR ^10, -SR ¹⁰ groups, a group -COOR ^10, -COR ¹⁰ group, a group _{^{-CON (R 10) 2 (R}} 10 is a hydrogen atom, an alkyl group, cycloalkyl group, aryl group, aralkyl group Etc.) and the like can be selected from a wide range.

Examples of R ¹ and R ² include linear or branched C _1-10 (for example, methyl, ethyl, propyl, isopropyl, butyl, s-butyl and t- Alkyl group, preferably a linear or branched C _1-6 alkyl group, more preferably a straight or branched C _1-4 alkyl group, etc.); A cycloalkyl group (e.g., a C _5-10 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group and the like); An aryl group (C _6-12 aryl group such as phenyl group, biphenyl group, naphthyl group and the like); Aralkyl group (C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group and the like); A linear or branched C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a n-butoxy group, an isobutoxy group and a t-butoxy group (for example, C _{1 -8} alkoxy group, preferably a C _1-6 alkoxy group), etc.); A cycloalkoxy group (e.g., a _C5-10 cycloalkoxy group such as a cyclohexyloxy group); An aryloxy group (e.g., a C _6-10 aryloxy group such as phenoxy group and the like); Aralkyloxy groups (for example, C _6-10 aryl-C _1-4 alkyloxy groups such as benzyloxy group and the like); An alkylthio group (C _1-10 alkylthio group) corresponding to the alkoxy group; A cycloalkylthio group (C _5-10 cycloalkylthio group) corresponding to the cycloalkoxy group; An arylthio group (C _6-10 arylthio group) corresponding to the aryloxy group; An aralkylthio group (C _6-10 aryl-C _1-4 alkylthio group) corresponding to the aralkyl group; An acyl group (e.g., a C _1-6 acyl group such as an acetyl group and the like); A carboxyl group; An alkoxycarbonyl group (e.g., a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group and the like); A halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); A nitro group; Cyano; A substituted amino group [a dialkylamino group (e.g., a di C _1-4 alkylamino group such as a dimethylamino group and the like), a dialkylcarbonylamino group (e.g., a di (C _1-4 alkyl-carbonyl ) Amino group)] and the like. The hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group, etc.) may have a substituent (an alkyl group or a halogen atom), and examples thereof include an alkylphenyl group (methylphenyl (tolyl) group, dimethylphenyl Or the like) may be formed.

Of these substituents R ¹ and R ² , preferred substituents R ¹ and R ² are an alkoxy group (straight chain or branched C _1-6 alkoxy group), an alkyl group (straight chain or branched C _1-6 alkyl group), an aryl group ( C _6-12 aryl group). Particularly preferred substituents R ¹ and R ² are C _1-4 alkyl group (straight or branched C _1-4 alkyl group such as methyl group) or aryl group (C _6-12 aryl group such as phenyl group). When the substituents R ¹ and R ² are aryl groups, the substituents R ¹ and R ² together with the ring Z ¹ and / or Z ² may form the ring-substituted areylene ring. The kinds of these substituents R ¹ and R ² may be the same or different in the same or different ring Z ¹ and / or Z ² .

In the present invention, at least one of the substitution numbers n1 and n2 of the hydroxyl group (phenolic hydroxyl group OH) is at least one integer. That is, in the host compound of the present invention, the ring Z ¹ and / or the ring Z ² have a phenolic hydroxyl group. n1 and n2 may be an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2 (for example, 1). n1 and n2 are in the ring Z ¹ and Z ^2, may be the same or different.

The substitution position of the hydroxyl group (phenolic hydroxyl group OH) is not particularly limited and may be substituted at appropriate positions of the ring Z ¹ and / or Z ² , for example, when the rings Z ¹ and Z ² are benzene rings Position, 2-position, 3-position, 4-position, or the like. When the rings Z ¹ and Z ² are naphthalene rings, they are often in the 5 to 8-positions of the naphthyl group. For example, condensed rings containing rings Ar ¹ and Ar ² (for example, 9 of fluorene) Position or 2-position of the naphthalene ring is substituted (in the case of 1-naphthyl or 2-naphthyl) in the naphthalene ring and the substitution position is 1,5-position, 2,6 - position and the like (particularly in the case of n1 and n2 being 1, the relation of 2,6-position). When n1 and n2 are 2 or more, the substitution position is not particularly limited. In the ring-linked arene ring Z ¹ and / or Z ² , the substitution position of the hydroxyl group is not particularly limited, and examples thereof include a condensed ring containing rings Ar ¹ and Ar ² (for example, 9-position, etc.) and / or an arene ring adjacent to the arene ring. For example, the 3-position or 4-position of the biphenyl rings Z ¹ and Z ² may be bonded to a condensed ring containing the rings Ar ¹ and Ar ² (for example, the 9-position of fluorene) , When the 3-positions of the biphenyl rings Z ¹ and / or Z ² are bonded to a condensed ring containing the rings Ar ¹ and Ar ² (for example, the 9-position of the fluorene), a hydroxyl group The substitution position of the substituent may be any of 2-, 4- to 6-position, and 2 'to 6'-position and is usually 4-, 5-, 6-, May be substituted at the 4-, 6-position, 4'-position (particularly, at the 6-position).

The substitution numbers m1 and m2 of the substituents R ¹ and R ² may be an integer of 0 to 4 (for example, 0 to 3), preferably 0 to 2 (for example, 1 or 2). Compounds whose substitution numbers m1 and m2 are an integer of 1 or more (for example, 1 or 2) are likely to stably incorporate the heterocyclic compound. m1 and m2, are the same or may differ in the ring Z ¹ and Z ^2.

Examples of the substituents R ³ and R ⁴ include the same hydrocarbon groups (alkyl group, cycloalkyl group, aryl group, aralkyl group) as the substituents R ¹ and R ² , an alkoxy group, a carboxyl group or a C _1-2 alkoxy- An atom, a nitro group, a cyano group or a substituted amino group.

The substitution numbers p1 and p2 are an integer of 0 to 4 (for example, 0 to 3), preferably 0 to 2 (for example, 0 or 1), particularly 0. The substitution numbers p1 and p2 may be the same as or different from each other, and when p1 and p2 are two or more, the types of the substituents R ³ and R ⁴ may be the same or different from each other. The substitution position of the substituents R ³ and R ⁴ is not particularly limited and, when the rings Ar ¹ and Ar ² are benzene rings, for example, a 2- to 7-position (2-position, / Or 7-position, etc.).

Representative compounds represented by the above formula (1) include the following compounds.

(A) a ring Ar ^One  And Ar ² Lt; RTI ID = 0.0 >

In the present invention, representative compounds represented by the formula (1) and used as a host molecule include 9,9-bis (hydroxyaryl) fluorenes in which the rings Ar ¹ and Ar ² are benzene rings. These compounds include (a1) 9,9-bis (hydroxyphenyl) fluorenes in which rings Z ¹ and Z ² are benzene rings and n 1 and n ² are ¹ in the formula (1); (a2) ring Z ¹ and Z ² is a naphthalene ring, a 9,9-bis (hydroxy-naphthyl), n1 and n2 are 1 fluorene and the like; (a3) ring Z ¹ and Z ² is a benzene ring, and the like 9,9-bis (poly-hydroxyphenyl) fluorene or more acids are n1 and n2 2.

(a1) 9,9-bis (hydroxyphenyl) fluorenes

As the 9,9-bis (hydroxyphenyl) fluorenes, compounds wherein R ¹ and R ² are hydrocarbon groups and m 1 and m 2 are 0 or 1 are suitably used.

Specific examples of the 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxyphenyl) ; (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy- Phenyl) fluorene, 9,9-bis (3-hydroxy-6-methylphenyl) fluorene, 9,9- 9,9-bis (C _1-6 alkylhydroxyphenyl) fluorene, etc.) such as 9,9-bis (alkylhydroxyphenyl) ; 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis 9,9-bis (dialkylhydroxyphenyl) fluorene (e.g., 9,9-bis (diC _1-6 alkylhydro Hydroxyphenyl) fluorene]; 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene 9,9-bis such as fluorene (cycloalkyl-hydroxyphenyl) fluorene [e.g., 9,9-bis (C _5-10 Cycloalkylhydroxyphenyl) fluorene, etc.]; 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene 9,9-bis such as fluorene (aryl-hydroxyphenyl) fluorene [e.g., 9,9-bis (hydroxy C _6-10 aryl Chlorophenyl) fluorene], and the like.

(a2) 9,9-bis (hydroxynaphthyl) fluorenes

Examples of the 9,9-bis (hydroxynaphthyl) fluorenes include 9,9-bis (hydroxynaphthyl) fluorenes in which the rings Z ¹ and Z ² of the 9,9-bis (hydroxyphenyl) fluorenes exemplified above are naphthalene rings, (5-hydroxynaphthyl) fluorene (for example, 9,9-bis (2-hydroxy-6-naphthyl) fluorene, 9,9- 9,9-bis (hydroxynaphthyl) fluorene and the like], and the like.

(a3) 9,9-bis (polyhydroxyphenyl) fluorenes

The 9,9-bis (polyhydroxyphenyl) fluorenes include the 9,9-bis (hydroxyphenyl) fluorenes [9,9-bis (monohydroxyphenyl) fluorenes] Corresponding fluorenes such as 9,9-bis (dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene (biscatechofluorene) and the like]; 9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene such as 9,9-bis (Di- or trihydroxyphenyl) fluorene (e.g., 9,9-bis (C _1-4 alkyl-dihydroxyphenyl) fluorene, etc.) Includes the oranges.

(B) Ring Ar ^One  And ring Ar ²  Is at least one compound selected from the group consisting of a naphthalene ring

(B1) benzofluorenes wherein one ring Ar ¹ is a benzene ring and the other ring Ar ² is a naphthalene ring, (b2) rings Ar ¹ and Ar ² are naphthalene Dibenzofluorene, and the like.

(b1) benzofluorenes

Examples of the benzofluorenes include 11,11-bis (hydroxyaryl) benzo [a] fluorenes, 11,11-bis (hydroxyaryl) benzo [b] (Hydroxyaryl) benzo [c] fluorenes.

Specifically, benzofluorenes in which Z ¹ and Z ² in the formula (1) are benzene rings and n 1 and n 2 are 1, for example, 11,11-bis (hydroxyphenyl) benzo [a] (Hydroxyphenyl) benzo [b] fluorenes, 7,7-bis (hydroxyphenyl) benzo [c] fluorenes; Z ¹ and Z ² is a naphthalene ring, a benzo n1 and n2 are 1 fluorene acids, for example, 11,11- bis (hydroxy-naphthyl) benzo [a] fluorene acids, 11,11- bis (hydroxymethyl Benzo [b] fluorenes, 7,7-bis (hydroxynaphthyl) benzo [c] fluorenes; Z ¹ and Z ² is a benzene ring, n1 and n2 is 2 or more benzo fluorene acids, for example, 11,11- bis (poly-hydroxyphenyl) benzo [a] fluorene acids, 11,11- bis (poly (Hydroxyphenyl) benzo [b] fluorenes, 7,7-bis (polyhydroxyphenyl) benzo [c] fluorenes and the like.

(b2) dibenzofluorenes

Representative dibenzofluorenes include 12,12-bis (hydroxyaryl) dibenzo [b, h] fluorenes.

Specifically, dibenzofluorenes in which Z ¹ and Z ² in the formula (1) are benzene rings and n 1 and n 2 are 1, for example, 12,12-bis (hydroxyphenyl) dibenzo [b , h] fluorenes; Dibenzofluorenes in which Z ¹ and Z ² are naphthalene rings and n 1 and n 2 are 1, for example, 12,12-bis (hydroxynaphthyl) dibenzo [b, h] fluorenes; Dibenzofluorenes in which Z ¹ and Z ² are benzene rings and n 1 and n 2 are two or more, for example, 12,12-bis (polyhydroxyphenyl) dibenzo [b, h] .

These host compounds may be used alone or in combination of two or more.

(Guest compound)

In the present invention, the compound used as the guest molecule may be a 5-membered or 6-membered heterocyclic ring containing a plurality of nitrogen atoms (for example, a basic nitrogen atom) or a heterocyclic compound having a condensed heterocycle thereof . The heterocyclic compound may be an aliphatic heterocyclic ring (non-aromatic heterocyclic ring) or an aromatic heterocyclic ring. In the heterocyclic compound, the number of nitrogen atoms (e.g., basic nitrogen atoms) forming a ring may be, for example, about 2 to 5, preferably about 2 to 4.

Such heterocyclic compounds include, for example, piperazine, N-aminoethylpiperazine, diethylenetriamine, triethylenediamine (DABCO; 1,4-diazabicyclo [2.2.2] octane) . A preferred heterocyclic compound (guest compound) may include, for example, a compound represented by the following formula (2).

(Wherein R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyano group or a triazine-alkyl group; R ⁶ to R ^{8 each} represent a hydrogen atom, a halogen atom, a nitro group, An alkyl group, an aryl group, an aralkyl group or an acyl group, the alkyl group may have a hydroxyl group, R ⁵ and R ⁶ may combine with each other to form a ring together with the adjacent nitrogen atom and carbon atom, q is 0 Or an integer of 1 to 3; and the double line of the solid line and the broken line represents a single bond or a double bond)

Examples of the alkyl group represented by R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- a linear or branched C _1-10 alkyl group such as an n-hexyl group, a nonyl group, an i-nonyl group and a decyl group. A preferred alkyl group may be a linear or branched C _1-6 alkyl group.

As the cycloalkyl group represented by R ⁵ , for example, a C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group can be exemplified. A preferable cycloalkyl group may be a C _5-8 cycloalkyl group, particularly a C _5-6 cycloalkyl group and the like.

The aryl group represented by R < ⁵ > may be a monocyclic or polycyclic aryl group, and the polycyclic aryl group may not only be fully unsaturated, but also partially saturated. As the aryl group, for example, a C _6-16 aryl group such as a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group and a tetralinyl group can be exemplified. The preferred aryl group may be a C _6-10 aryl group (phenyl group, naphthyl group, etc.).

The aralkyl group (arylalkyl group) represented by R ⁵ is a group in which the aryl group and the alkyl group are bonded, and examples thereof include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 1-phenyl- A C _6-12 aryl C _1-6 alkyl group such as a naphthalene-2-ylethyl group, a 1- (naphthalene-2-yl) -n-propyl group or an inden-1- _ylmethyl group . A preferred aralkyl group may be a C _6-10 aryl C _1-4 alkyl group (benzyl group, phenethyl group, etc.).

The alkyl group, cycloalkyl group, aryl group and aralkyl group may have a substituent. Examples of the substituent include a halogen atom (such as a fluorine atom and a chlorine atom), a hydroxyl group, an alkoxy group (such as a C _1-6 alkoxy group such as a methoxy group or an ethoxy group), an acyl group (formyl group; (Such as a C _1-10 alkyl-carbonyl group such as an _octyl group and the like), a carboxyl group, an alkoxycarbonyl group (a C _1-4 alkoxy-carbonyl group and the like) and an alkyl group (a C _1-6 alkyl group such as a methyl group and an ethyl group)

In the triazine-alkyl group represented by R ⁵ , triazine may be 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, or the like, An amino group, a hydroxyl group, or the like may be substituted. Examples of typical triazine-alkyl groups include 4,6-diamino-1,3,5-triazine-2-methyl group, 4-amino- Triazine-2-C _1-4 alkyl groups such as methyl group and 4,6-dihydroxy-1,3,5-triazine-2-methyl group. A preferred triazine-alkyl group may be 4,6-diamino-1,3,5-triazine-2-C _1-2 alkyl.

Preferred R ⁵ is 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 cyanoethyl group or a 1,3,5-triazine-2-C _{1- 2} alkyl group, and the like, and it is often a hydrogen atom, a cyanoethyl group or the like in many cases.

The halogen atom represented by R ⁶ to R ⁸ includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group represented by R ⁶ to R ⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- an n-hexyl group, a 2-ethylhexyl group, a nonyl group, an i-nonyl group, a decyl group, a lauryl group, a tridecyl group, a myristyl group, a pentadecyl group, a palmityl group, a heptadecyl group, A linear or branched C _1-20 alkyl group (for example, a C _1-18 alkyl group). The preferred alkyl group may be a C _1-12 alkyl group (e.g., a C _1-10 alkyl group). The alkyl group may have a hydroxyl group. As the alkyl group having a hydroxyl group, for example, a hydroxy C _1-20 alkyl group (e.g., a hydroxy C _1-18 alkyl group) such as a hydroxymethyl group, a hydroxyethyl group and the like can be mentioned. The preferred hydroxyalkyl group may be a hydroxyC _1-6 alkyl group (e.g., a hydroxyC _1-2 alkyl group) such as a hydroxymethyl group.

As the cycloalkyl group, aryl group and aralkyl group represented by R ⁶ to R ⁸ , the same groups as the substituent R ⁵ can be exemplified.

The acyl group represented by R ⁶ to R ⁸ may be a group in which a carbonyl group is bonded to an organic group such as a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. As the acyl group, for example, a formyl group; 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 decanoyl group, a 3-methylnonanoyl group, -Ethyl octanoyl group, 3,7-dimethyloctanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, 1-methylpentadecanoyl group, 14 -Methylpentadecanoyl group, a 13,13-dimethyltetradecanoyl group, a heptadecanoyl group, a 15-methylhexadecanoyl group, an octadecanoyl group, a 1-methylheptadecanoyl group, a nonadecanoyl group, A C _1-26 alkyl-carbonyl group such as a _diazo , a _{henacycloamino} group or the like; A C _2-6 alkenyl-carbonyl group such as acryloyl group, methacryloyl group, allylcarbonyl group, and cinnamoyl group; A C _2-6 alkynyl-carbonyl group such as an ethynylcarbonyl group and a propynylcarbonyl group; A C _6-18 aryl-carbonyl group such as a benzoyl group, a naphthylcarbonyl group, a biphenylcarbonyl group, and an anthranylcarbonyl group; (For example, a nonaromatic or aromatic 5-membered or 6-membered heteroaryl-carbonyl group) such as a 2-pyridylcarbonyl group or a thienylcarbonyl group. A preferable acyl group may be a C _1-20 alkyl-carbonyl group (for example, a C _1-6 alkyl-carbonyl group and the like) and the like.

R ⁵ and R ⁶ may combine with each other to form a ring (for example, a 4 to 12 membered ring, preferably a 5 to 10 membered ring) together with the adjacent nitrogen atom and carbon atom.

q represents 0 or an integer of 1 to 3, and usually 0 to 2 (for example, 0 or 1).

The double bond of the solid line and the broken line represents a single bond or a double bond and may be a single bond when R ⁵ and R ⁶ are bonded to each other to form a ring (heterocycle), and R ⁵ and R ⁶ may form a ring (heterocycle) May be double bonded.

Preferable R ⁶ may be a hydrogen atom, an alkyl group, an aryl group or the like, and may be an alkyl group. Preferable R ⁷ and / or R ⁸ may be a hydrogen atom, an alkyl group, or a hydroxyalkyl group.

More specifically, the heterocyclic compound as the guest compound may include, for example, a compound represented by the following formula (2a) and / or a compound represented by the following formula (2b).

(In the formula, r represents an integer of 0 to 5; R ⁵ to R ⁸ and the double line of the solid line and the broken line are the same as above)

and r may be an integer of 0 to 5, for example, 1 to 5 (for example, 1 to 4).

Specifically, examples of the compound (imidazole compound) represented by the formula (2a) include imidazole; 1-alkylimidazole such as 1-methylimidazole; 2-alkylimidazole such as 2-methylimidazole, 2-heptadecylimidazole and 2-undecylimidazole; 2-arylimidazole such as 2-phenylimidazole; 4-alkylimidazole such as 4-methylimidazole; 1,2-dialkylimidazole such as 1,2-dimethylimidazole; 1-aralkyl-2-alkylimidazole such as 1-benzyl-2-methylimidazole; 1-cyanoethyl-2-alkylimidazole such as 1-cyanoethyl-2-methylimidazole and 1-cyanoethyl-2-undecylimidazole; 1-cyanoethyl-2-arylimidazole such as 1-cyanoethyl-2-phenylimidazole; 1-aralkyl-2-arylimidazole such as 1-benzyl-2-phenylimidazole; 2,4-dialkylimidazole such as 2-ethyl-4-methylimidazole; 2-aryl-4-alkylimidazole such as 2-phenyl-4-methylimidazole; 1-cyanoethyl-2, 4-dialkylimidazole such as 1-cyanoethyl-2-ethyl-4-methylimidazole; 2-aryl-4-alkyl-5-hydroxyalkylimidazole such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; And 2-aryl-4,5-dihydroxyalkylimidazole such as 2-phenyl-4,5-dihydroxymethylimidazole. Further, the imidazole compound often has at least one substituent among R ⁵ to R ⁸ in many cases.

Among these compounds, imidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2- 2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole or 2 Phenyl-4,5-dihydroxymethylimidazole and the like are preferable.

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

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

In the inclusion compound, the ratio of the guest compound to 1 mole of the host compound is 0.5 to 5 moles, preferably 0.7 to 2.5 moles (for example, 0.75 to 2.3 moles), more preferably 0.8 to 2.2 moles For example, 1 to 2 moles).

In the inclusion compound of the present invention, the phenolic hydroxyl group may form a salt (for example, a salt with a base). The inclusion compound of the present invention includes compounds in which such a salt is formed as long as it has an inclusion form.

(Production method of inclusion compound)

The inclusion compound of the present invention can be produced by mixing or reacting the compound represented by the formula (1) (host compound) with the heterocyclic compound (guest compound). Further, when at least one of the host compound and the guest compound is a liquid at a mixing temperature (for example, at room temperature or about 30 to 100 ° C), the other component may be added to and mixed with the other component. For example, when the guest compound is a liquid, the inclusion compound can be obtained by adding a host compound to the guest compound, mixing (or stirring) as necessary, and recovering the compound by filtration or the like. In the case of mixing or stirring under heating, the mixture is cooled and recovered to obtain an inclusion compound.

The mixing or reaction of the host compound and the guest compound may be carried out in the presence of a solvent, if necessary. Examples of the solvent include alcohols such as methanol, ethanol, propanol and butanol; Ethers such as cellosolves such as 2-methoxyethanol (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve) and ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol Carbitols such as monomethyl ether (methylcarbitol), diethylene glycol monoethyl ether (ethylcarbitol) and diethylene glycol monobutyl ether (butyl carbitol), cyclic ethers such as dioxane and tetrahydrofuran, di Chain ethers such as ethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 2-hexanone, isophorone, and cyclohexanone; Esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and isobutyl acetate; Ether esters such as ethylene glycol monoethyl ether acetate (ethyl cellosolve acetate), diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate; Aliphatic hydrocarbons such as heptane and octane; Alicyclic hydrocarbons such as cyclohexane; Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; Amides such as dimethylformamide and dimethylacetamide; And sulfoxides such as dimethyl sulfoxide and the like. The solvent may be an aprotic polar solvent such as amides, sulfoxides and the like. These solvents may be used alone or in combination of two or more.

The ratio of the host compound to the guest compound may be about 0.5 to 5 moles, preferably 0.7 to 3 moles, more preferably 0.8 to 2.5 moles, of the guest compound per 1 mole of the host compound.

The mixture containing the solvent, the host compound and the guest compound is mixed while stirring as required, and the resulting solid is collected by filtration or the like to obtain the inclusion compound. The mixed solution may be mixed under heating, and the heating temperature may be about 30 to 120 캜 (preferably 50 to 100 캜) or less, for example, below the boiling point of the solvent. After heating, it may be cooled if necessary, and the resulting solid may be recovered.

After completion of the reaction, the solvent may be distilled off by a conventional method such as atmospheric distillation or vacuum distillation, if necessary, before the solid is recovered. The reaction mixture containing the solvent may be mixed with a solvent different from the reaction solvent to precipitate the inclusion compound.

The recovered inclusion compound may be washed or dried if necessary.

In the inclusion compound of the present invention, the composition ratio of the host compound and the guest compound can be easily determined by an analytical method for common use, for example, the integral ratio of ¹ H-NMR spectrum. Further, the composition ratio of the host compound and the guest compound may be determined based on the amount of the guest compound released from the inclusion compound by heating by thermogravimetric analysis (TG-DTA). In the present invention, the composition ratio between the host compound and the guest compound of the inclusion compound may be determined so as to be the simplest integer ratio from the results of analysis by ¹ H-NMR spectrum and / or TG-DTA.

The inclusion compound structure of the present invention can be determined by methods such as single crystal X-ray structural analysis, powder X-ray diffraction, and the like.

(Curable composition)

The inclusion compound of the present invention is stable over a long period of time at a low temperature (room temperature or storage temperature) even when mixed with an epoxy resin in order to stably encapsulate a heterocyclic compound functioning as a curing agent of the epoxy resin. On the other hand, since the inclusion compound releases a heterocyclic compound upon heating, the epoxy resin can be rapidly cured when heated to a predetermined temperature. In addition, the inclusion compound of the present invention can function as a curing accelerator in addition to functioning as a curing agent for an epoxy resin, because it has a tertiary amino group together with a primary amino group or a secondary amino group. Therefore, the inclusion compound of the present invention is useful as (A) a curing agent and / or a curing accelerator for curing (B) an epoxy resin (epoxy compound). Further, (A) an inclusion compound (a curing agent and / or a curing accelerator) is useful for producing a curable composition in combination with (B) an epoxy resin (epoxy compound).

The curable composition may contain the above inclusion compound and an epoxy resin, and if necessary, may contain a conventional epoxy resin curing agent and / or a curing accelerator (curing agent for curing and / or curing accelerator) (Or epoxy group) of the epoxy resin to cure the epoxy resin, and the curing accelerator is not particularly limited as long as it is a compound accelerating the curing reaction. Examples of such curing agents or curing accelerators include amine compounds (aliphatic amines, alicyclic and heterocyclic amines, aromatic amines, modified amines, etc.), imidazole compounds, imidazoline compounds, amide compounds, ester compounds , A phenolic compound, an alcohol compound, a thiol compound, an ether compound, a thioether compound, a urea compound, a thiourea compound, a Lewis acid compound, a phosphorus compound, an acid anhydride compound, An initiator), an active silicon compound-aluminum complex, and the like.

Specifically, as the curing agent and the curing accelerator, for example, the following compounds may be mentioned.

Examples of the aliphatic amines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, pentanediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, 2,5- Straight-chain or branched alkylenediamines such as 2,5-hexanediamine; Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, and pentamethyldiethylenetriamine; N, N-dialkylaminoalkylamines such as dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine and N, N-dimethylcyclohexylamine, or N, N-dialkylaminocycloalkylamines; (Poly) ether diamines such as bis (2-dimethylaminoethyl) ether, diethylene glycol bispropylamine and polypropylene glycol diamine; Alkyl esters such as N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N ' Substituted alkylenediamines; Alkanolamines such as dimethylaminoethoxyethoxyethanol, triethanolamine and dimethylaminohexanol; Mono-t-alkylamine, and the like.

Examples of alicyclic and heterocyclic amines include piperidine, piperazine, menthenediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N- (aminoethyl) piperazine, trimethylaminoethylpiperazine, N, Mono-cyclic amines such as N'-dimethylpiperazine and 4-amino-2,2,6,6-tetramethylpiperidine; Bis (aminocyclohexyl) alkanes such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; Triazines such as N, N ', N "-tris (dimethylaminopropyl) hexahydro-s-triazine; 1,4-diazabicyclo (2,2,2) octane (triethylenediamine) -Bis (3-aminopropyl) -2,4,8,10-tetaspiro [5,5] undecane or its adduct, DBU (1,8-diazabicyclo [5.4.0] And cyclic cyclic amines such as DBN (1,5-diazabicyclo [4.3.0] -5-nonene).

Examples of the aromatic amines include aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, bis (4-amino- Tris (aminomethyl) benzene, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethyl Aminomethyl) phenol, phthalocyanine tetramine, benzylmethylamine, dimethylbenzylamine, pyridine, picoline, and? -Methylbenzylmethylamine.

Examples of the modified amines include polyamines in which an amine is added to an epoxy compound (epoxy adduct), Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone blocking polyamines (ketimines), dicyandiamides, guanidines, Hydrazide, diaminomalonitrile, amine imide, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, and the like.

Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, Imidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, But are not limited to, sol, 1-n-butyl imidazole, 2-n-butyl imidazole, 1-isobutyl imidazole, 2-isobutyl imidazole, Imidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole Isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Methyl-2-methyl-3-benzylimidazolium chloride, 1- (2-cyanoethoxy) methylimidazole, 1- Benzyl-2-phenylimidazole hydrochloride, and the like.

As the imidazoline-based compound, for example, 2-methylimidazoline, 2-phenylimidazoline and the like can be given.

Examples of the amide compound include condensation products of dimer acid (polymerized fatty acid or higher fatty acid) (for example, dimer to tetramer of unsaturated higher fatty acid) and polyamines (e.g., alkylene diamine, polyethylene polyamine, etc.) And polyamide (polyaminoamide) obtained by the above method.

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

Examples of the phenol compound include phenol resins such as aralkyl type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin, phenol novolac resins and novolak type phenol resins such as cresol novolac resin, Resins, for example, phenolic resins such as epoxidized or butylated novolac phenolic resins; Modified phenol resins such as dicyclopentadiene-modified phenol resin, para-xylene-modified phenol resin, triphenolalkane-type phenol resin, and multifunctional phenol resin. Examples of the alcohol compounds, thiol compounds, ether compounds and thioether compounds include polyols, polymercaptans, polysulfides, 2- (dimethylaminomethyl), phenol 2,4,6-tris Aminomethyl) phenol, and 2,4,6-tris (dimethylaminomethyl) phenol; and the like.

Examples of the urea compound, thiourea compound and Lewis acid compound include butylated urea, butylated melamine, butylated thiourea and boron trifluoride.

As the phosphorus compound, an organic phosphine compound, for example, primary phosphines such as alkylphosphine such as ethylphosphine and butylphosphine, and arylphosphine such as phenylphosphine; Dialkylphosphines such as dimethylphosphine, dipropylphosphine and methylethylphosphine; second phosphines such as diphenylphosphine; And tertiary phosphines such as trimethylphosphine, triethylphosphine and triphenylphosphine.

Examples of the acid anhydride compound include, for example, phthalic anhydride, trimellitic anhydride, chlorinated anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris Aromatic polycarboxylic acid anhydrides such as trimellitic anhydride and hydrotrimellitate; (E.g., 4-methylhexahydrophthalic anhydride, etc.), endomethylenetetrahydrophthalic anhydride, methylendomethyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like. Alicyclic polycarboxylic acid anhydrides such as methylcyclohexene tetracarboxylic acid anhydride, anhydride hymic acid, anhydrous methyl hymic acid, and anhydrous methyl nadic acid; Aliphatic polycarboxylic acid anhydrides such as maleic anhydride, dodecenylsuccinic anhydride, polyadipic acid anhydride and polyazelaic acid anhydride.

Examples of the onium salt compound and the active silicon compound-aluminum complex include aryldiazonium salts, diaryliodonium salts, arylsulfonium salts, arylmethylsulfonium salts (benzylmethylsulfonium salts and the like), diarylsulfonium salts, Aluminum complexes, triphenylmethoxysilane-aluminum complexes, silylperoxide-aluminum complexes, triphenylsilanol-tris (salicylaldehyde) aluminum complexes, and the like.

These curing agents and / or curing accelerators may be used alone or in combination of two or more. Of these curing agents and curing accelerators, phenol compounds and acid anhydride compounds are generally used. Therefore, the curable composition of the present invention may contain at least one compound selected from phenol compounds (for example, novolak phenol resin and the like) and acid anhydride compounds, and may have heat resistance (glass transition temperature, (E.g., bending properties at a high temperature environment (e.g., 260 占 폚)], it is preferable to use an acid anhydride compound (for example, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, And the like).

The ratio of the inclusion compound (first curing agent) and the curing agent and / or the curing accelerator (second curing agent) may be appropriately selected depending on the kind of the second curing agent, the functional group equivalent (hydroxyl group equivalent, acid anhydride group equivalent, etc.) For example, the former / latter (weight ratio) = 100/0 to 30/70, preferably 100/0 to 50/50, and more preferably about 100/0 to 70/30. When the second curing agent is an acid anhydride compound, the ratio of the inclusion compound (first curing agent) to the second curing agent is, for example, from 70/30 to 1/99 (weight / weight ratio) , 50/50 to 3/97), preferably 30/70 to 5/95 (for example, 20/80 to 7/93). When the second curing agent is a phenol compound, the ratio of the inclusion compound (first curing agent) to the second curing agent is, for example, from 70/30 to 1/99 (weight / weight ratio) 50/50 to 5/95), preferably 30/70 to 10/90 (for example, 20/80 to 12/88).

When the second curing agent is used, the ratio of the functional group (for example, acid anhydride group, hydroxyl group, etc.) capable of reacting with the epoxy group in the second curing agent is preferably from 0.7% May be about 1.3 equivalents (e.g., 0.8 to 1.2 equivalents), preferably about 0.9 to 1.1 equivalents, and usually about 1 equivalent.

The epoxy resin (B) may be an epoxy compound obtained by oxidizing a glycidyl ether, a glycidyl ester, a glycidyl amine or an unsaturated double bond by epoxidation.

As the glycidyl ether type epoxy compound (or resin) in the epoxy resin (B), for example, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, Glycidyl ether compounds of alkane monoesters such as cidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether and stearyl glycidyl ether; Polyglycidyl ethers of alkane polyols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycols, thiodiglycol, glycerin, trimethylol propane, pentaerythritol and sorbitol, and bisphenols such as bisphenol A Polyglycidyl ethers of alkylene oxides (such as ethylene oxide) adducts; Polyglycidyl ether compounds of monocyclic polyhydric phenols such as hydroquinone, resorcin, pyrocatechol, and fluoroglucinol; Dihydroxynaphthalene, biphenol, diphenylalkane [methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol A (bisphenol A), isopropylidene bis ), Tetrabromobisphenol A, 1,3-bis (4-hydroxycylbenzene), 1,4-bis (4-hydroxycylbenzene), 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- (Dimethylphenyl) fluorene, 9,9-bis (6-hydroxy-2-naphthyl) fluorene and the like], 9,9-bis (hydroxy (mono- or poly) alkoxyaryl) fluorenes , 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene, etc.] , Tri- or tetraphenylalkane [1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra Phenyl) ethane, etc.], diphenyl ketone, diphenyl ether, diphenyl thioether, diphenyl sulfone, novolak or novolac resins (phenol novolak, orthocresol novolak, ethyl phenol novolac, butylphenol novolak, octyl Phenol novolac, resorcinol novolac, etc.), terpene phenol and other polyglycidyl ether compounds of polynuclear polyhydric phenols; Polyglycidyl ether compounds of heterocyclic compounds such as triglycidyl isocyanurate, and the like.

Examples of the glycidyl ester type epoxy compound (or resin) include monoglycidyl ester compounds of monocarboxylic acids such as glycidyl esters of bosaccharide; There may be mentioned acid addition salts such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimeric acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Homopolymers or copolymers of glycidyl esters and glycidyl (meth) acrylates of aliphatic, alicyclic or aromatic polycarboxylic acids such as maleic acid, maleic acid, maleic acid, maleic acid, maleic acid, Can be exemplified.

Examples of the glycidylamine type epoxy compound (or resin) include N, N-diglycidyl aniline, bis (4- (N-methyl-N-glycidylamino) Glycidyl amine compounds of amines such as diglycidyl toluidine, tetraglycidyldiaminodiphenyl methane, triglycidyl aminophenol and the like.

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

These epoxy compounds (or resins) may be used alone or in combination of two or more. In addition, the epoxy compound (or resin) may be a monomer, or may include a dimer of about a dimer to a 10-dimer. In addition, mono- or polyglycidyl ethers of alkane monols or alkane polyols, glycidyl esters of monocarboxylic acids, and epoxides of cyclic olefins are often used as a reactive diluent.

Preferable examples of the epoxy compound (or resin) include polyglycidyl ether compounds having a plurality of epoxy groups (or oxirane rings) in the molecule such as methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (Bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), 9,9-bis (hydroxyaryl) fluorene, 9,9- ) Polyglycidyl ether of a bisphenol compound such as fluorene.

The epoxy resin may be a liquid having fluidity at room temperature (15 to 20 ° C), a semi-solid or solid having a high viscosity (or high viscosity) which lacks fluidity, and usually has a fluidity at a temperature (processing temperature) And may be a liquid or viscous liquid epoxy resin at a mixing temperature or may be a liquid or viscous epoxy resin at room temperature (15 to 20 ° C).

In the curable composition of the present invention, the amount of the inclusion compound to be used may be such that the heterocyclic compound as the guest compound is usually used as a curing agent and / or a curing accelerator depending on the curing method. For example, in the case of a addition-type curing agent in which a curing agent molecule is always incorporated into a curing resin by reaction with an epoxy group, the amount of the inclusion compound to be used is usually in the range of from 1 mol of the epoxy group (or oxirane ring) (For example, about 0.2 to 0.8 mol, preferably about 0.25 to 0.5 mol) in terms of a guest compound or a heterocyclic compound (a curing agent and / or a curing accelerator) enclosed. Further, in the case of using as a polymerization type curing agent, a photo initiating type curing agent, a curing accelerator, or the like which causes the ring opening of the epoxy group catalytically without incorporating the curing agent molecule into the curing resin and causes the polymerization addition reaction between the epoxy compounds, The amount of the inclusion compound to be used may be 1 mole or less (for example, about 0.001 to 0.5 mole, preferably about 0.005 to 0.1 mole) based on 1 mole of the epoxy group (or oxirane ring) in terms of the guest compound or the heterocyclic compound.

The amount of the inclusion compound to be used is, for example, from 0.1 to 25 parts by weight, preferably from 0.5 to 15 parts by weight, more preferably from 1 to 10 parts by weight (for example, For example, 1.5 to 5 parts by weight).

The fluorene compound as the host compound has high compatibility with the epoxy resin and also has high dispersibility in the non-decomposable additive. Therefore, even when the curable resin composition contains the fluorene compound, the properties of the cured product are not adversely affected.

The curable composition of the present invention can be produced by mixing the component (A) and the component (B). For example, an epoxy resin (epoxy compound) (and optionally, the second curing agent and various additives described below) (A), an inclusion compound (a curing agent and / or a curing accelerator component) and (B) Mixing or kneading at a temperature or a time at which the curing reaction (or gelation) does not occur or can be suppressed by using a mixer or a mixer, a kneader (nipper, roll, extruder, etc.) or a grinding machine For example, melt kneading, etc.), the curable composition of the present invention can be produced. The mixing or kneading may be carried out under heating (for example, about 50 to 100 占 폚) or may be carried out by mixing or kneading at a low temperature (for example, from room temperature to 50 占 폚, preferably from room temperature to 40 占 폚) The mixing or kneading under heating may be omitted. The component (A) and the component (B) may be mixed or kneaded in the presence of the same organic solvent as described above.

The curable composition of the present invention may contain various additives such as a silane coupling agent, a plasticizer, an organic solvent, a reactive diluent, a filler, a reinforcing agent, a coloring agent (pigment), a flame retardant, a releasing agent, a stabilizer (an antioxidant, ), An extender, a thickener, and the like may be added.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane (Aminoethyl)? -Aminopropyltrimethoxysilane,? - aminopropyltrimethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyltrimethoxysilane, N- aminopropyltrimethoxysilane,? (aminoethyl)? -aminopropyltriethoxysilane, N-phenyl-? -aminopropyltrimethoxysilane, N-phenyl-? -aminopropyltriethoxysilane,? -mercaptopropyltrimethoxysilane, gamma -mercaptopropyltriethoxysilane, and the like. Examples of the plasticizer include phthalic acid plasticizers, alkane dicarboxylic acid plasticizers such as adipic acid, phosphoric acid ester plasticizers, and polyester plasticizers.

Examples of the organic solvent include the above-exemplified solvents. Examples of the reactive diluent include the epoxy compounds exemplified above, such as n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl Epoxy compounds such as dibutyl ether, dicyclopentadiene epoxide and phenols such as phenol, cresol, t-butylphenol and the like.

Examples of the filler include fillers such as calcium bicarbonate, light calcium carbonate, natural silica, synthetic silica, fused silica, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc, kaolin, clay, mica, wollastonite, titanium Potassium carbonate, aluminum potassium carbonate, aluminum borate, sepiolite, zonectite and the like. The colorant may be a black pigment such as carbon black, a white pigment such as titanium oxide, a yellow pigment, an orange pigment, a red pigment, a purple pigment, a blue pigment, or a green pigment. Examples of the reinforcing agent include organic fibers (such as natural fibers such as cellulose fibers (cellulose nanofibers), synthetic fibers such as polyalkylene arylate fibers, vinylon fibers and aramid fibers), inorganic fibers ] Can be exemplified.

Examples of the release agent include fatty acid-based releasing agents (higher fatty acids, higher fatty acid esters, higher fatty acid calcium and the like), waxes (such as carnauba wax and polyethylene wax), silicone oils and the like.

Examples of the flame retardant include hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodi (Tribromophenoxy) triazine, ethylene bis tetrabromophthalimide, polybromophenyl indane, brominated polystyrene, tetrabromobisphenol A polycarbonate , Brominated compounds such as phenylene bromide and the like, brominated compounds such as phenylene bromide, brominated phenylene ethylene oxide and polypentabromobenzyl acrylate, triphenylphosphate, tricresylphosphate, tricresylphosphate, cresyldiphenylphosphate, xylyldiphenylphosphate, 2-ethylhexyldiphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bis (Dicyclohexyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dicyclohexylphosphine) Phosphoric acid esters such as phosphoric acid esters such as phosphoric acid esters such as phosphoric acid esters such as phosphoric acid esters such as phosphoric acid esters such as phosphoric acid esters, Surface treated hydrous metal compounds of tartaric acid, magnesium hydroxide surface-treated with nickel compounds, magnesium hydroxide surface treated with silicone polymer, procobite, multi-layer surface treated hydrated metal compounds, and cationic polymer-treated magnesium hydroxide.

The curable composition of the present invention may further contain an elastomer (or an elastomer modifier) such as acrylonitrile butadiene rubber (NBR), liquid polybutadiene, polybutadiene (butadiene rubber, BR), chloroprene rubber, silicone Rubber, modified silicone rubber, crosslinked NBR, crosslinked BR, acrylic rubber (including core-shell acrylic rubber), urethane rubber, polyester elastomer, liquid NBR with functional group, liquid polyester, liquid polysulfide, urethane prepolymer .

If necessary, a resin other than an epoxy resin such as an olefin resin (high density polyethylene, polypropylene, etc.), a styrene resin (polystyrene and the like), an acrylic resin (such as polymethyl methacrylate) (Nylon 6, nylon 66, etc.), a polyurethane resin, a silicone resin, etc., and the resin may be an engineering plastic such as a polyolefin resin or a polyolefin resin such as polyethylene terephthalate, (Polybutylene terephthalate, polyethylene naphthalate, bisphenol A type polycarbonate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetheretherketone, etc.).

The amount of these additives, elastomer and resin to be used is not particularly limited and may be selected depending on the application.

The present invention also includes a cured product wherein the curable composition is cured. Such a cured product can be prepared by heating and curing the curable composition according to the use of the curable composition. For example, the curable composition may be applied to a substrate to be cured, or it may be cured by injection or sealing into a preform, may be molded and cured, impregnated with a substrate (fiber substrate) to prepare a prepreg, The legs may be laminated by a method such as overlapping or winding, and the legs may be formed into a predetermined shape and cured. The curing can be carried out at a temperature at which the guest compound can be released from the inclusion compound, and may be, for example, about 100 to 250 占 폚 (preferably 120 to 200 占 폚, more preferably 130 to 180 占 폚).

Although the cured product thus obtained contains a host compound which is a low molecular compound, the cured product has various physical properties (for example, mechanical properties such as bending strength, flexural modulus, dynamic viscoelasticity, glass transition temperature, (Or maintain) without significantly changing (or decreasing) the electrical properties such as thermal properties, dielectric constant, dielectric tangent, absorption rate, and the like. Therefore, the curable composition of the present invention can be effectively stored with high stability while suppressing deterioration of physical properties in the cured product.

Example

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.

^{The 1} H-NMR was measured by dissolving the inclusion compound in a medium of chloroform, medium methanol, or heavy dimethylsulfoxide and using "AVANCE III HD" ( ¹ H resonance frequency: 300 MHz) manufactured by Bruker BioSpin.

TG-DTA was measured using "EXSTAR 6000 TG / DTA 6200" manufactured by Seiko Instruments Inc.

1. Preparation of inclusion compounds

[Example 1] (Synthesis of inclusion compound of BCF: 2E4MZ)

To a solution of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (BCF, manufactured by Osaka Gas Chemical Co., Ltd., 3.78 g, 10 mol) in ethyl acetate (10 mL) -Methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., 2.30 g, 2.1 mmol) was added thereto. After stirring for 1 hour, heating was stopped and the reaction mixture was cooled to room temperature. The resulting solid was filtered out and dried to obtain a product (white solid, yield: 3.66 g). It was confirmed by the ¹ H-NMR and TG-DTA that the inclusion compound obtained was an inclusion compound having a porosity ratio BCF: 2E4MZ = 1: 1.

Fig. 1 shows the ¹ H-NMR spectrum of the inclusion compound of Example 1, and Fig. 2 shows a TG-DTA chart of the inclusion compound of Example 1. Fig. In the ¹ H-NMR spectrum, the ordinate indicates the intensity and the abscissa indicates the unit ppm. On the TG-DTA chart, the abscissa indicates the temperature (占 폚), the ordinate on the left side indicates DTA, Quot; TG ", a TG (thermogravimetric analysis) chart is shown by a solid line, and a DTA (differential thermal analysis) chart is shown by a broken line. In the TG-DTA chart, " Cel " means " C ".

[Example 2] (Synthesis of inclusion compound of BXF: 2E4MZ)

To a suspension of ethyl acetate (15 mL) of 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (BXF, manufactured by Osaka Gas Chemicals K.K., 4.05 g, 10 mmol) (White solid, yield: 4.18 g) was obtained in the same manner as in Example 1, except that ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., 2.26 g, 2.1 mmol) was added. It was confirmed by the ¹ H-NMR and TG-DTA that the inclusion compound obtained was an inclusion compound having a porosity ratio BXF: 2E4MZ = 1: 1.

Fig. 3 shows the ¹ H-NMR spectrum of the inclusion compound of Example 2, and Fig. 4 shows a TG-DTA chart of the inclusion compound of Example 2.

[Example 3] (Synthesis of inclusion compound of BNF: 2E4MZ)

To a methanol (4 mL) solution of 9,9-bis (6-hydroxynaphthalen-2-yl) fluorene (BNF, manufactured by Osaka Gas Chemical Co., Methyl imidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., 444 mg, 4 mmol) was added thereto. After stirring for 1 hour, the reaction mixture was added to water (50 mL), and the resulting solid was filtered and dried to give the product (white solid, yield 712 mg). It was confirmed by the ¹ H-NMR and TG-DTA that the inclusion compound obtained was an inclusion compound having a porosity BNF: 2E4MZ = 1: 1.

FIG. 5 shows the ¹ H-NMR spectrum of the inclusion compound of Example 3, and FIG. 6 shows the TG-DTA chart of the inclusion compound of Example 3.

[Example 4] (Synthesis of inclusion compound of BCF: 2MZ-H)

2-methylimidazole (2MZ-H, 1.81 g, 22 mol) was added to a solution of BCF (3.78 g, 10 mmol) in ethyl acetate (15 mL) at 70 ° C. After heating for 5 minutes, the mixture was cooled, and the resulting solid was filtered and dried to obtain the product (white solid, yield 3.00 g). ^It was confirmed by ¹ H-NMR and TG-DTA that it is an inclusion compound having a porosity ratio BCF: 2MZ-H = 1: 2.

FIG. 7 shows the ¹ H-NMR spectrum of the inclusion compound of Example 4, and FIG. 8 shows the TG-DTA chart of the inclusion compound of Example 4.

[Example 5] (Synthesis of inclusion compound of BXF: 2MZ-H)

2-methylimidazole (2MZ-H, 1.81 g, 22 mol) was added to a solution of BXF (4.07 g, 10 mmol) in ethyl acetate (15 mL) at 70 占 폚. After heating for 100 minutes, the mixture was cooled, and the resulting solid was filtered and dried to give the product (white solid, yield 3.91 g). ^It was confirmed by ¹ H-NMR and TG-DTA that it is an inclusion compound having a porosity BXF: 2MZ-H = 1: 1.

FIG. 9 shows the ¹ H-NMR spectrum of the inclusion compound of Example 5, and FIG. 10 shows the TG-DTA chart of the inclusion compound of Example 5.

[Example 6] (Synthesis of inclusion compound of BCF: DBU)

To the solution of BCF (377 mg, 1 mmol) in ethyl acetate (8 mL) was added diazabicyclo undecene (DBU, manufactured by Tokyo Kasei K.K., 344 g, 2.6 mmol). The mixture was heated and stirred at 100 占 폚 in a vessel while preventing the DBU from leaking, and then cooled. The resulting solid was filtered and dried to obtain a product (white solid, yield 660 mg). ^It was confirmed by ¹ H-NMR and TG-DTA that it is an inclusion compound having a porosity ratio BCF: DBU = 1: 2.

Fig. 11 shows the ¹ H-NMR spectrum of the inclusion compound of Example 6, and Fig. 12 shows the TG-DTA chart of the inclusion compound of Example 6.

Table 1 shows the composition of each inclusion compound and the release temperature of the guest compound.

2. Preparation of curable compositions and their properties

[Example 7: Curable composition]

13.3 parts by weight (3 parts by weight as 2E4MZ) of the inclusion compound (BCF: 2E4MZ) obtained in Example 1 was added to 100 parts by weight of liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) Manufactured by Nippon Seisakusho Seisakusho Co., Ltd., ACE Homogenizer AM-10) at a rotation number of 15,000 rpm for 10 minutes to prepare a curable composition.

[Comparative Example 1: Curing Composition]

3 parts by weight of 2E4MZ was added to 100 parts by weight of a liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation), and a curable composition was prepared in the same manner as in Example 7. [

[Measurement of gelation time]

According to JIS C 2161, a sample is placed on a stainless steel plate heated to a predetermined temperature and mixed with a spatula in a circular shape at a rate of 60 times per minute, so that the sample becomes gel-like and the sample does not adhere to the spauler The end point was defined as the point at which no sagging occurred. As shown in Table 2, the curable composition of Example 7 exhibited a gelation time equivalent to that of Comparative Example 1.

[DSC measurement of the curable composition]

Using 100 parts by weight of liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation) and the inclusion compound (3 parts by weight as imidazole) obtained in Examples 2 to 3, The compositions (the curing compositions of Examples 8 and 9) were prepared. As a control, the curable composition of Comparative Example 1 was used.

A part of the curable composition was taken in an aluminum pan and subjected to thermal analysis using a differential scanning calorimeter DSC ("EXSTAR 6000 DSC 6220" manufactured by Seiko Instruments Inc.). The results are shown in Table 3. Fig. 13 is a DSC chart of the curable composition of Example 7, Fig. 14 is a DSC chart of the curable composition of Example 8, Fig. 15 is a DSC chart of the curable composition of Example 9, ≪ / RTI > In the DSC chart, " Cel " means " C ".

As is clear from Table 3 and Figs. 13 to 16, the curable composition using the inclusion compound of the examples showed a sharp exothermic peak, but the curable composition of Comparative Example 1 using imidazole exhibited a plurality of exothermic peaks broadly .

[Storage stability of curable composition]

The container containing the curable composition was kneaded while cooling with ice water, and the mixture was allowed to stand at 25 占 폚 for 20 minutes. Thereafter, a part of the composition was sampled and used an E-type viscometer ("TVE-22L" , And the viscosity (mPa · s / 25 ° C) was measured at a predetermined time at 25 ° C. The results are shown in Table 4.

From Table 4, the viscosity of the curable composition of Example 1 was about twice that of the initial value after 48 hours, whereas the viscosity of the curable composition of Comparative Example 1 was 7 times of the initial value after 24 hours.

3. Preparation of cured product and measurement of physical properties

According to the following procedure, a hardened test piece was prepared.

[Example 10: Preparation of hardness test piece]

100 parts by weight of a liquid epoxy resin (jER 828, manufactured by Mitsubishi Chemical Corporation) and 10 parts by weight of the inclusion compound (BCF: 2E4MZ) obtained in Example 1 were added to a brain ball (Ishikawa-style stirring brain No. 18, (Inclusive of silicone rubber having a diameter of? 3 mm or 4 mm as a spacer) between two sheets of aluminum foil (3 mm in thickness) with cellophane, a clasp compound was dispersed in an epoxy resin, ], And cured in a hot-air circulating oven under the conditions shown in Table 5 below. Further, the diameter of the spacer was appropriately changed according to the size of the test piece.

[Comparative Example 2: Preparation of hardened test piece]

100 parts by weight of a liquid epoxy resin (jER 828) and 3 parts by weight of 2-ethyl-4-methylimidazole (2E4MZ) were well mixed using a stirrer. This was degassed by vacuum, poured into a cell for casting, and cured under the conditions shown in Table 5 in a hot air circulating oven.

[Example 11: Preparation of hardened test piece]

100 parts by weight of a liquid epoxy resin (jER 828) and 10 parts by weight of an inclusion compound (BCF: 2E4MZ) obtained in Example 1 were kneaded using a brain globe (Ishikawa-style stirring brain No. 18, Ishikawa Kojo Co., Ltd.) , 86.3 parts by weight of an acid anhydride-based compound (MH-700, manufactured by Shin-Nippon Rikagaku Co., Ltd., acid anhydride equivalent: 164 g / eq.) Was added and mixed with a spatula. After degassing under vacuum, the mixture was poured into a casting mold, In a hot air circulating oven under the conditions described in Table 5 below. In addition, the acid anhydride compound was compounded at a ratio of 1 mole of the acid anhydride group of the acid anhydride compound to 1 mole of the epoxy group of the epoxy resin.

[Comparative Example 3: Preparation of hardened test piece]

100 parts by weight of liquid epoxy resin (jER 828), 3 parts by weight of 2-ethyl-4-methylimidazole (2E4MZ) and 86.3 parts by weight of an acid anhydride compound (MH-700) were mixed well using a spatula. This was poured into a cell for casting by vacuum degassing and cured under the conditions described in Table 5 in a hot air circulating oven. In addition, the acid anhydride compound was compounded at a ratio of 1 mole of the acid anhydride group of the acid anhydride compound to 1 mole of the epoxy group of the epoxy resin.

[Example 12: Preparation of hardened test piece]

54.2 parts by weight of a phenolic compound (PSM-4261, phenol resin, hydroxyl equivalent weight: 103 g / eq.) And 10 parts by weight of the inclusion compound (BCF: 2E4MZ) (6-inch mixing roll DY6-15, manufactured by DAIHAN Co., Ltd.) at 100 占 폚, and 100 parts by weight of liquid epoxy resin (jER828) was added and kneaded for about 5 minutes. After being taken out from the roll, it was heated at 100 DEG C, poured into a casting mold cell, and cured under the conditions shown in Table 5 in a hot air circulating oven. The phenol compound was compounded at a ratio of 1 mole of the hydroxyl group of the phenol compound to 1 mole of the epoxy group of the epoxy resin.

[Comparative Example 4: Preparation of hardened test piece]

100 parts by weight of a liquid epoxy resin (jER 828) and 54.2 parts by weight of a phenolic compound (PSM-4261) were kneaded at 90 to 100 캜 with a biaxial roll. After removing from the roll, 3 parts by weight of 2-ethyl-4-methylimidazole (2E4MZ) was added, and the mixture was heated in an oven at 100 DEG C and mixed with a spatula, poured into a mold shell, In the conditions shown in Table 5 below. The phenol compound was compounded at a ratio of 1 mole of the hydroxyl group of the phenol compound to 1 mole of the epoxy group of the epoxy resin.

Table 5 shows the compounding ratio of each cured product and curing conditions.

Various physical properties of the cured products obtained in Examples 10 to 12 and Comparative Examples 2 to 4 were measured by the methods described below.

[Bending Test]

Test piece: about 80 mm x 10 mm x 4.0 mm

Measurement conditions: test speed 2 mm / min;

           Distance between points 64mm

           Test temperature Room temperature or 260 ° C

Measuring device: universal material tester 5582 type (manufactured by Instron)

The bending elastic modulus was calculated from the tangential elastic modulus of the initial straight portion.

[Measurement of dielectric constant and dielectric tangent]

Test method: Cavity resonant perturbation method (in accordance with ASTM D 2520)

Test piece: 80 mm x 1.5 mm x 1.5 mm thick

Measurement conditions: Frequency 1GHz

           Test environment 23 ± 2 ℃, 50 ± 5% RH

           Number of measurements n = 2

Measurement apparatus: PNA-L network analyzer N5230A (manufactured by Agilent Technologies)

           Cavity resonator CP431 (Kanto Denshio Co., Ltd.).

[Thermomechanical analysis (TMA) measurement]

Measuring conditions: Measuring temperature Room temperature to 300 ° C

           Heating rate 5 ° C / min

           (50 mL / min)

           Measuring mode Compression mode (load 20mN)

Measuring device: TMA 8310 (Rigaku Co., Ltd.).

[Dynamic viscoelasticity (DMA) measurement]

Measurement items: E ', E ", tanδ

Test piece: Strip 50mm × 10mm × 3mm

Measuring conditions: Measuring temperature Room temperature to 300 ° C

           Heating rate 4.0 ° C / min

           Frequency 1Hz

           In an atmospheric nitrogen stream (300 mL / min)

           Measuring mode Bending mode

Measurement apparatus: EXSTAR DMS6100 (manufactured by Hitachi High-Tech Science Co., Ltd.).

[Absorption rate measurement]

Test piece: about 50 mm x 50 mm x 3.0 mm

Test method: The test piece was dried under the following conditions, immersed in water, and the difference between the weight of the test piece after immersion and the weight of the test piece after pre-drying was calculated by dividing the weight by the weight of the test piece after the pre-drying.

Measurement conditions: pre-drying 50 ° C x 24h

           Immersion in water 23 ° C × 24h

           Number of measurements n = 3.

The measurement results of various physical properties are shown in Table 6 below.

From the results shown in Table 6, the cured product of the curable composition containing the inclusion compound of the present invention exhibited almost the same physical property values as the cured product of the curable composition containing the imidazole compound alone. Therefore, by using the inclusion compound of the present invention, a curable composition having high storage stability can be obtained without significantly impairing physical properties.

In Example 11 containing an acid anhydride compound, unlike the other Examples, the flexural strength and flexural modulus at 260 占 폚 were higher than those of Comparative Example 3, the glass transition temperature was increased by 10 占 폚 or more , Heat resistance was improved.

In the present invention, the storage stability of a curable composition containing an epoxy resin is improved in order to form an inclusion compound, and furthermore, it exhibits a property of being rapidly cured by heating. Therefore, the curable composition of the present invention can be used for various applications to which an epoxy resin is applied, for example, insulating materials, sealing materials (sealing materials for electronic parts such as semiconductors and light emitting diodes such as semiconductor sealing materials) A laminated board with a substrate such as a laminated board, a glass cloth, a paper, a synthetic fiber cloth, and a copper foil such as a laminate for a printed wiring board), a composite material (a fiber reinforced composite with a reinforcing fiber such as glass fiber, carbon fiber or aramid fiber) A coating material such as a mold material, a mold material, a repair material for a concrete structure, an adhesive, a varnish, a paint (including a powder coating), and an ink.

Claims (15)

An inclusion compound comprising, as a guest compound, a compound represented by the following formula (1) as a host compound and a compound having a 5 or 6-membered heterocyclic ring containing a plurality of nitrogen atoms or a condensed heterocyclic ring thereof as a constituent atom of a ring.

^{(Wherein, Ar 1, Ar 2, Z} 1 and Z ² are each the same or different and each represents a monocyclic arene ring or polycyclic arene ^{ring; R 1, R 2, R} 3 and R ⁴ are the same or each or M1, m2, p1 and p2 are the same or different from each other, and n1 and n2 are the same or different and each represent an integer of 0 to 4, at least one of n1 and n2 is an integer of at least 1, An integer of 0 to 4) The compound according to Claim 1, wherein in Formula (1), Ar ¹ and Ar ² are the same or different and each is a benzene ring or a naphthalene ring; Z ¹ and Z ² are the same or different and are a benzene ring or a naphthalene ring; R ¹ and R ² are the same or different and 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 cyano group or a substituted amino group; R ³ and R ⁴ are the same or different and are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group; n1 and n2 are the same or different and are an integer of 1 to 3; m1 and m2 are the same or different and are an integer of 0 to 2; p1 and p2 are the same or different and each is an integer of 0 to 2; 3. A method according to claim 1 or 2, wherein the formula (1) according to, Ar ¹ and Ar ² is a benzene ring; Z ¹ and Z ² are a benzene ring or a naphthalene ring; n1 and n2 are 1 or 2; R ¹ and R ² are the same or different and each is a C _1-4 alkyl group or a C _6-10 aryl group, m 1 and m 2 are integers of 0 to 2; and p1 and p2 are 0. 4. The inclusion compound according to any one of claims 1 to 3, wherein R ¹ and R ² are a methyl group or a phenyl group and m 1 and m 2 are 1 or 2 in the formula (1). The inclusion compound according to any one of claims 1 to 4, wherein the guest compound comprises a compound represented by the following formula (2).

(Wherein R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a cyano group or a triazine-alkyl group; R ⁶ to R ^{8 each} represent a hydrogen atom, a halogen atom, a nitro group, An alkyl group, an aryl group, an aralkyl group or an acyl group, the alkyl group may have a hydroxyl group, R ⁵ and R ⁶ may combine with each other to form a ring together with the adjacent nitrogen atom and carbon atom, q is 0 Or an integer of 1 to 3; and the double line of the solid line and the broken line represents a single bond or a double bond) 6. The inclusion compound according to any one of claims 1 to 5, wherein the guest compound comprises a compound represented by the following formula (2a) and / or (2b).

(Wherein r represents an integer of 0 to 5; R ⁵ to R ⁸ and the double line of the solid line and the broken line are the same as those of the fifth aspect) 7. The inclusion compound according to any one of claims 1 to 6, wherein the inclusion compound contains a guest compound in a proportion of 0.5 to 5 moles relative to 1 mole of the host compound. A compound represented by the formula (1) described in claim 1 and a compound having a 5-membered or 6-membered heterocyclic ring or a condensed heterocyclic ring containing a plurality of nitrogen atoms as a constituent atom of a ring, ≪ RTI ID = 0.0 > 1, < / RTI > A curing agent or curing accelerator comprising the inclusion compound according to any one of claims 1 to 7 as a curing agent or curing accelerator for curing an epoxy resin. A curable composition comprising an inclusion compound according to any one of claims 1 to 7 and an epoxy resin. The curable composition according to claim 10, wherein the epoxy resin is a liquid epoxy resin. 12. The curable composition according to claim 10 or 11, wherein the curable composition comprises an inclusion compound in an amount of 0.1 to 25 parts by weight based on 100 parts by weight of the epoxy resin. The curable composition according to any one of claims 10 to 12, further comprising at least one compound selected from phenolic compounds and acid anhydride compounds. 14. The cured composition according to any one of claims 10 to 13, wherein the cured composition is a cured product. A method for producing a cured product by heating the curable composition according to any one of claims 10 to 13 to cure the composition.

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