TW201139358A - Clathrate and method for producing same - Google Patents

Abstract

In order to provide a highly pure 1:2 clathrate of an aromatic carboxylic acid compound and an imidazole compound, and to provide an epoxy resin composition containing said clathrate as a curing agent or a curing promoter, it is possible to produce a highly pure clathrate that contains an aromatic carboxylic acid compound (A) and an imidazole compound (B) and where the mole ratio of (A) to (B) is 1:2, by means of adding the aromatic carboxylic acid compound to an alcohol solution of the imidazole compound, or by adding an alcohol solution of the aromatic carboxylic acid compound to the imidazole compound. The clathrate obtained thereby is useful as a curing agent or a curing promoter for epoxy resins or the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel inclusion compound and a method for producing the same, which relates to an aromatic acid-containing compound which can be used as an epoxy resin hardening catalyst and the like. The inclusion compound of the oxime compound and the method for producing the same, and the epoxy resin composition containing the inclusion compound or a cured product thereof. The present application claims priority from Japanese Patent Application No. 2010-228645, filed on Jan. 20, 2010, filed on Jan. In this article. [Prior Art] Epoxy resins are widely used in various fields because of their excellent mechanical properties and thermal properties. As the curing agent for curing the epoxy resin, an imidazole-based compound is used, but the mixture of the epoxy resin and the imidazole-based compound has a problem that the curing starts earlier and the stability of the single liquid is extremely poor. Therefore, for the hardener, a salt to which a hydroxybenzoic acid is added to an imidazole-based compound has been proposed (refer to the patent literature), or a tetraphenol-based compound (for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) is used. Ethane (hereinafter referred to as TEp is an inclusion body of an imidazole-based compound (see Patent Document 2). Although the imidazolium acid addition salt or the inclusion body exhibits a certain effect, it is expected to develop the same. The functional person or function is further improved. Therefore, the industry has developed and developed an inclusion compound containing the present dicarboxylic acid compound represented by the following formula (i) and the imidazole compound represented by the following formula (ii) (patent Literature 3), 153278.doc 201139358 [Chemical]

COOH

[wherein, Ri represents a C1-C6 alkyl group, a C1 to C6 alkoxy group, a nitro group or a hydroxyl group] [Chemical 2]

Wherein R 2 represents a hydrogen atom, a C1 to C10 alkyl group, an aryl group, an arylalkyl group or a cyanoethyl group; R3 to Rs each independently represent a hydrogen atom, a nitro group, a halogen atom, and a C1 which may have a substituent; C20 alkyl, C1-C20 alkyl, aryl, arylalkyl or C1 to C20 thiol group substituted by a radical. The inclusion compound in the patent document 3 is produced by adding an isophthalic acid compound and a sodium salic compound to a solvent, and then performing a heat treatment or a heat reflow treatment while precipitating it as needed. In addition, it is preferable to dissolve the phthalic acid compound represented by the formula (1) and the imidazole compound represented by the formula (ii) in a solvent, respectively, in consideration of the solubility in a solvent. Further, the solutions are mixed with each other. However, Patent Document 3 does not specifically describe the inclusion compound of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole, and if 153278. Doc •4· 8 201139358 By reacting 5-hydroxyl-p-dicarboxylic acid with 2-phenyl-4-methyl-5-hydroxymethylimidazole by the method described in the patent document, only one of the two compounds is obtained. : 1 a mixture of a compound and a 1:2 inclusion compound. Further, although it has been possible to produce a ruthenium-containing compound of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole in high purity (Patent Document 4), it has not been high. Purity manufacturing 1: 2 inclusion compound. CITATION LIST Patent Literature Patent Literature 1: Patent Publication No. 4-2638 Patent Document 2: Japanese Patent Laid-Open No. Hei 11-71449, Patent Document 3: International Publication No. 2008/075427, Patent Document 4: International Publication 2009/ SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION Therefore, the object of the present invention is to obtain an aromatic carboxylic acid compound such as 5-hydroxyisophthalic acid and 2-phenyl-4-mercapto-5 in high purity. - 1 : 2 inclusion compound of imidazoles such as hydroxymethylimidazole. Means for Solving the Problems The inventors of the present invention have diligently studied and found that by repeatedly improving the mixing method of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxydecyl imidazole An inclusion compound having a molar ratio of 1 to 2 (hereinafter referred to as a 1:2 inclusion compound) is obtained. Further research was carried out, and it was found that the hostation of the inclusion compound by the inclusion compound (hereinafter referred to as 1:1 inclusion compound) with a molar ratio of only 1:1 to the known host and guest 153278.doc 201139358 The compound and the guest compound can be produced into a 1:2 inclusion compound by the production method of the present invention. Further, when a compound which can be produced by a known production method can be produced and compared with the case where it is impossible to manufacture, it is found that the solubility of the aromatic carboxylic acid compound as a main compound in a solvent is poor, and it is known. The method cannot produce i ·· 2 inclusion compounds. At the same time, it is now possible to manufacture a curable epoxy resin composition containing the 1:2 inclusion compound and its hardened material 'and found that its characteristics are improved compared with the case of containing i : i inclusion compound' invention. That is, the present invention relates to the following: (1) an inclusion compound or a composition thereof containing a compound comprising a aromatic acid compound (A) and a compound represented by the following formula (11); and (a) (7)) The inclusion ratio of the molar ratio of 1:2, and the inclusion compound accounts for 70 mol/0% of the total inclusion compound of (4) and (B), [Chemical 3]

(wherein R 2 represents a hydrogen atom 'C1 to C10 alkyl, aryl, arylalkyl or cyanoethyl' r3 to r5 represent a hydrogen atom, a nitro group, a sulfonium atom, a nominee group, a trans-substituted group C1 to C20, aryl, arylalkyl or C1 to C20, the dotted line represents a single bond or a double bond. (2) The inclusion compound or the composition thereof according to (1) above, Wherein the aromatic carboxylic acid compound is a compound represented by the following formula (III) or the following formula (IV), 153278.doc _6_ 8 201139358

(COOH)n1 (ΙΠ) [Chemical 4] (^6) η2 (wherein nl represents any integer from 1 to 4; n2 represents any integer from 0 to 4; and R6 represents a C1 to C6 alkyl group, Nitro or hydroxy) [Chem. 5] (^7) m2 - (COOH) ml (17) (wherein 'ml denotes any integer from 1 to 4; denotes any integer from 〇~2; R7 denotes C1 ~C6 alkyl, nitro, hydroxy or the group represented by the following formula, [Chemical 6] ^

(COOH) qr dicentric μ q table or an integer of 2; * represents a bonding position)); (3) a compound of the following formula (I), or a combination thereof, wherein the above formula (IV) is [Chemistry 7]

153278.doc 201139358

(wherein, Ri represents a Cl~C6 alkyl group, a C1 to C6 alkoxy group, a nitro group); I () an inclusion compound of the above (3) or a composition thereof, wherein the above formula (5-hydroxyisophthalene) The inclusion compound of any one of the above-mentioned items (1) to (4), or a composition thereof, wherein the above formula (II) is a 2-phenylmethyl-5-yl-methyl group Further, the present invention relates to the following: (6) A method for producing an inclusion compound according to the above (1) or a composition thereof, which comprises adding an aromatic group to an alcohol liquid of the compound of the above formula (II) (7) The method for producing an inclusion compound according to the above (1) or a composition thereof, which comprises adding an alcohol solution of an aromatic carboxylic acid compound to the compound of the above formula (II); (8) A curable epoxy resin composition or a cured product thereof, comprising the inclusion compound according to any one of the above (1) to (5), or a composition thereof, and an epoxy resin. (Inclusion compound or composition thereof) The inclusion compound of the present invention or a composition thereof is an aromatic carboxylic acid compound (hereinafter referred to as "carboxylic acid compound" As the host compound, an imidazole compound or an imidazoline compound represented by the following formula (II) (hereinafter abbreviated as a sodium compound) is used as a guest compound, and the molar ratio of the carboxylic acid compound to the carbazole compound is only 1 : 2 encapsulated compound' or a composition containing a molar ratio of 1:2 inclusive compound, 153278.doc 8 201139358 [Chemical 8] R4 Rs Η (Π) 丫, r2 r3 (in the formula R2 represents a hydrogen atom, a C1~C-based group, an aryl group, an arylalkyl group or an arylethyl group 'r3~r5" represents a hydrogen atom, a nitro group, a dentate atom, a ci~c2 fluorene group, and is substituted by a thiol group. a C1-C20 alkyl group, an aryl group, an arylalkyl group or a C1 to C20 fluorenyl group; a dotted line representing a single bond or a double bond carboxylic acid compound and an imidazole compound having a molar ratio of 1:2 The inclusion compound of different molar ratios such as 1: i may be mixed in the present invention, and is referred to as a composition of the above-mentioned inclusion compound in the present invention. The inclusion compound of the present invention or a composition thereof contains a carboxylic acid. In the total inclusion compound of the compound and the imidazole compound, 丨: 2 inclusion compound The content ratio is 7 〇 mol% or more, preferably 8 〇 mol% or more, more preferably 90 mol%. More preferably, it is substantially not mixed with i :] and other other molar ratios In the compound, the inclusion compound of the present invention may contain a solvent such as a solvent, and the third component of the composition is preferably 40 mol% or less, more preferably 1 mol% or less, and most preferably no third. The inclusion compound of the component. The term "encapsulated compound" in the present invention means that the host compound forms an inclusion lattice, and the host compound is bonded by a bond other than a covalent bond to a species or two or more guest compounds. The material 'is more preferably a crystalline compound. The inclusion compound of the present invention containing a slow acidifying compound and (4) a compound may also be referred to as a salt formed from the compound of (4) and a compound of the formula. 153278.doc 201139358 As abbreviated as ' 5-perylene isophthalic acid is called "mpA", 2_phenyl ice methyl-5-hydroxymethylimidazole is called "2p4MHz". The term "encapsulated crystal lattice" as used herein means that the host compounds are bonded to each other by a bond other than a covalent bond, and a covalent bond is used in a gap of two or more molecules of the bonded host compound. The bond is bound to other molecules (guest or solvent, etc.), or other molecules and host compounds; or the host compound is bonded to other molecules (guests or solvents, etc.) by bonds other than covalent bonds, and bonds with other molecules In the gap of 2 or more molecules of the host compound, the host compound and/or other molecules (guest or solvent, etc.) are encapsulated by a bond other than the covalent bond. The inclusion compound of the present invention can be used as a hardener for resins such as polyester resins, epoxy resins, epoxy-polyacetal resins, and the like, and is particularly suitable as a hardener for epoxy resins. The sulphur epoxy resin composition can be suitably used for curing an epoxy resin, for example, an epoxy resin adhesive, a semiconductor sealing material, a liquid crystal sealing material, a laminated board for printed wiring, a varnish, (10) a material, and an ink. And other uses. ’ ' The inclusion compound of the present invention may be a liquid which is dissolved in a solvent, but is preferably a powder (precipitated in a solvent). By making it into a powder form, it can be used, for example, for a powder coating. The structure of the inclusion compound can be confirmed by thermal analysis (TG and DTA), infrared absorption spectroscopy (IR), X-ray diffraction (XRD) pattern, solid state NMR spectroscopy, and the like. Also, the composition of the inclusion compound can be analyzed by thermal analysis! It was confirmed by h_Nmr spectrum, high performance liquid chromatography (HPLC), elemental analysis, and the like. Further, when the ratio (purity) of the 1:2 inclusion compound is, for example, a composition comprising a 1:1 inclusion compound and a 1:2 inclusion compound, it may be 153278.doc, 10. 201139358 according to the purity (%) ==: 2 inclusion compound / (1 : i inclusion compound + i: 2 inclusion compound) x 100, calculated from the integral value of lH_NMR of the inclusion compound. As an example, the purity of the HIPA and 2P4MHZ: 2, the purity of the inclusion compound can be obtained by dividing the integral value of the hunger (10) 6 by the integral value of ppm (a), and obtaining it according to the following formula. 1. The purity (%) of the inclusion compound (2a/n> xi 〇〇 (carboxylic acid compound) The aromatic carboxylic acid compound is not particularly limited, and examples thereof include the following: benzoic acid, 2-methyl Benzoic acid, 3-mercaptobenzoic acid, 4·methylbenzoic acid, 2-ethyl benzoic acid, 3-ethylbenzoic acid, 4·ethylbenzoic acid, 2-n-propylbenzoic acid, 3-positive Propyl benzoic acid, 4-n-propylbenzoic acid, 2-butylphthalic acid, 3-butylphthalic acid, 4-butylbenzoic acid, 2-isopropylbenzoic acid, 3-isopropyl Benzoic acid, 4-isopropylbenzoic acid, 2-isobutylphthalic acid, 3-isobutylphthalic acid, 4-isobutylbenzoic acid, 2-perbenzoic acid, 3-hydroxybenzene Formic acid, 4-hydroxybenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2-nitrobenzoic acid decyl ester, methyl 3-nitrobenzoate, Methyl 4-nitrobenzoate, ethyl 2-nitrobenzoate, ethyl 3-nitrobenzoate, 4-nitrobenzoic acid, 2-nitrobenzoic acid C, 3-stone Schiffki propyl formate, 4-stone succinyl propyl acrylate, 2-succinyl benzoate, butyl 3-nitrobenzoate, 4-nitro Butyl phthalate, 2,3-dimethylbenzoic acid, 2,4-dimercaptoic acid 2,5-dimercaptobenzoic acid, 2,6-dimercaptobenzoic acid, 3, 4-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, 3,6-dimethylbenzoic acid, 4,5-dimercaptobenzoic acid, 4,6-dimethylbenzoic acid , 2,3-diethyl 153278.doc 201139358 benzoic acid, 2,4-diethylbenzoic acid, 2,5-diethylbenzoic acid, 2,6-diethylbenzoic acid, 3,4 -diethylbenzoic acid, 3,5-diethylbenzoic acid, 3,6-diethylbenzoic acid, 4,5-diethylbenzoic acid, 4,6-diethylbenzoic acid, 2, 3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxyindole acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-di Hydroxybenzoic acid, 3,6-dihydroxybenzoic acid, 4,5-dihydroxyindole acid, 4,6-dihydroxybenzoic acid; phthalic acid, 3-methylphthalic acid, 4-mercaptophthalic acid, 5-methylphthalic acid, 6-methylphthalic acid, 3-ethylphthalic acid, 4-ethylphthalic acid, 5-ethyl O-phthalic acid, 6-ethylphthalic acid, 3-n-propylphthalic acid, 4-n-propylphthalic acid Formic acid, 5·n-propyl phthalic acid, 6-n-propylphthalic acid, 3-butylphthalic acid, 4-butylphthalic acid, 5-butylphthalic acid , 6-butylphthalic acid, 3-isopropylphthalic acid, 4-isopropylphthalic acid, 5-isopropylphthalic acid, 6-isopropylphthalic acid, Isobutylphthalic acid, 4-isobutylphthalic acid, 5-isobutylphthalic acid, 6-isobutylphthalic acid, 3-hydroxyphthalic acid, 4_super Base of stearic acid, 5-hydroxyphthalic acid, 6-hydroxyphthalic acid, 3,4-dihydroxyphthalic acid, 3,5-dihydroxyphthalic acid, 3,6_two Hydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 4,6-dihydroxyphthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, 5-nitrogen Phthalic acid, 6-nitrophthalic acid, 3,4·dimethyl phthalic acid, 3,5-didecyl phthalic acid, 3,6-dimethyl phthalene Formic acid, 4,5-dimethylphthalic acid, 4,6-dimercaptophthalic acid; 153278.doc 12 • · 8 201139358 isophthalic acid, 2-methyl Isophthalic acid, 4-methylisophthalic acid, 5-methylisophthalic acid, 6-mercaptoisophthalic acid, 2-ethylisophthalic acid, 4-ethylisophthalic acid Dicarboxylic acid, 5-ethyl meta-dicarboxylic acid, 6-ethyl isophthalic acid, 2-n-propyl isophthalic acid, 4-n-propylisophthalic acid, 5-n-propyl isophthalic acid ,6-n-propylisophthalic acid, 2-isopropylisophthalic acid, 4·isopropylisophthalic acid, 5-isopropylisophthalic acid, 6-isopropylisophthalic acid Dicarboxylic acid, 2-butylisophthalic acid, 4-butylisophthalic acid, 5-butyl meta-2-decanoic acid, 6-butylisophthalic acid, isobutyl phthalic acid, 4-isobutylisophthalic acid, 5-isobutylisophthalic acid, 6-isobutyl meta-succinic acid, 4-tert-butylisophthalic acid, 5_third Base meta-benzoic acid, 6_t-butyl isophthalic acid, 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 6-hydroxy-p-dicarboxylic acid, 2'4-dihydroxyisophthalic acid, 2,5-dihydroxyisophthalic acid, 2,6-dihydroxyisophthalic acid, 4,5•dihydroxyisophthalic acid, 4, 6_ Dihydroxyisophthalic acid, 5,6-dihydroxymethanedicarboxylic acid, 2,4·dimethylm-xylylene phthalate, 2,5-dimethylisophthalic acid, 2,6-didecyl Meta-xylylene I 4,5-methyl-m-phthalic acid, 4,6-diindenyl stearic acid, 5'6--methylisophthalic acid, 2•nitro-m-xylylene phthalate, Substituted stearic dicarboxylic acid, 5-nitroisophthalic acid, "Schiffki dibenzoic acid, 2-methyl-p-phenylene terephthalate, 2. ethyl terephthalic acid, 2-n-propyl-p-benzene Dicarboxylic acid, isopropyl terephthalic acid, 2-butylene terephthalic acid, 2 • isobutyl palladium: formic acid, 2-transbasic p-dicarboxylic acid, 2,6-di-p-phenyl-p-dicarboxylic acid, a : methyl-p-xylylene phthalate, 2-nitroterephthalic acid, 1,2,3-benzenetricarboxya ruthenium 1,2'4-benzonic acid (stanoic acid), benzenetricarboxylic acid , υ, 4·笨 153278.doc 13· 201139358 Two oxic acid, loading, the present dicarboxylic acid, 3-hydroxy-1,2,4-benzenetricarboxylic acid, 5-di-oroxic acid, 6·yl-based- 1,2,4-benzenetricarboxylic acid, 12,4,5-benzenetetracarboxylic acid (pyromellitic acid); , formic acid 2-naphthoic acid, 2-methyl-1-naphthoic acid, 3-methyl -1-naphthyl:, 4-methyl-1-naphthoic acid," Naphthoic acid, "basinnaphthalene:,7·mercapto-1_naphthoic acid, 8-methylq•naphthoic acid, methyl-methyl-naphthylmethyl-2_naphthoic acid, 4-mercapto _2-naphthoic acid, 5-methyl-2-naphthoquinone, 6'methyl·2·naphthoic acid, 7-methyl-2•naphthoic acid, 8-methyl-2-naphthoic acid, 1'2 -naphthalene dicarboxylic acid, hydrazine, 3-naphthalene dicarboxylic acid, quinone-naphthalene dicarboxylic acid, iota, 5-naphthalenedicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 〗 7, 7-naphthalenedicarboxylic acid, hydrazine , 8_naphthalene dicarboxylic acid, 2'3 naphthalene dicarboxylic acid, 2,4-naphthalene dicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene Carboxylic acid, 2,8-naphthalene dicarboxylic acid, 2-hydroxy-ι-naphthoic acid, 3-hydroxy-1-naphthoic acid, 4-hydroxy-1-naphthoic acid, 5-hydroxynaphthoic acid, cardioside-1 -naphthoic acid, 7-hydroxy-1-naphthoic acid, 8-hydroxy-1.naphthoic acid, dipyridyl-2-naphthoic acid, 3-carbyl-2-naphthoic acid, 4-pyridyl-2-naphthoquinone Acid, 5-cyano-2-naphthoic acid, 6-carbyl-2-naphthoic acid, 7-carbyl-2-naphthoic acid, 8-hydroxy-2-naphthoic acid, 1,2,4,5-naphthalene Carboxylic acid, 2,3-dihydroxynaphthoic acid, 2,4-dihydroxy-1-naphthoic acid, 2,5-dihydroxy-1-naphthoic acid, 2,6-di-yl-1-naphthoic acid, 2 , 7-two classics -1-naphthoic acid, 2,8-di-trans-yl-naphthoic acid, 3,4-dihydroxy-1.naphthoic acid, 3,5-dihydroxy-1-naphthoic acid, 3,6-di Base-1-caincarboxylic acid, 3,7-di-propyl-1-naphthoic acid, 3,8-di-trans-yl-naphthoic acid, 4,5-di-trans-naphthoic acid, 4,6- Di-mercapto-1-naphthoic acid ' 4,7-di-propyl-1-naphthoic acid, 4,8-di-yl-1-naphthoic acid, 5,6-dipyridyl-i-naphthoquinone 153278.doc -14- 201139358 酉文,5,7·dihydroxy-1·naphthoic acid, 5,8-dihydroxy-1-naphthoic acid, 6,7-dihydroxy_1~naphthoic acid, 6,8-dihydroxy_ Ι_naphthoic acid, 7,8-dihydroxy-1_naphthoic acid, indole 3-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 1,5-hydroxyhydroxynaphthoic acid, 1,6-dihydroxy-2-naphthoic acid, 1,7-dihydroxy-2-naphthoic acid, 1,8-dihydroxy-2-naphthoic acid, 3,4-dihydroxy-2-naphthoic acid, 3 , 5· monohydroxy-2-naphthoic acid, 3,6-dihydroxy-2-naphthoic acid, 3,8-dihydroxy-2•naphthyl, 4 < dihydroxy-2-naphthoic acid, 4, 6_Dihydroxy_2_naphthoic acid, 4,7-hydroxy-2-naphthoic acid, 4,8-dihydroxy-2-naphthoic acid, 5,6-dihydroxy-2-naphthoic acid, 5,7-di Hydroxy-2-naphthoic acid, 5,8-dihydroxy-2-naphthoic acid, 6,7-monohydroxy-2-naphthoic acid, 6,8-dihydroxy-2-naphthoic acid, 7,8-dihydroxy-2_cacocarboxylic acid, cyclohexanecarboxylic acid, hydrazine, 2•cyclohexanedicarboxylic acid, hydrazine , 3_cyclohexanedicarboxylic acid, hexamethylene acid, hydrazine, 1·cyclohexanedicarboxylic acid, 1,2-decahydronaphthalene dicarboxylic acid, l3-decahydronaphthalene dicarboxylic acid, 〖, 4_decahydrogen Naphthalene dicarboxylic acid, 1,5-decahydronaphthalene dicarboxylate, decahydronaphthalene dicarboxylic acid, 1,7-decahydronaphthalene dicarboxylic acid, hydrazine, 8-decahydronaphthalene dicarboxylic acid, and the like. It is also possible to use two kinds of these aromatic carboxylic acid compounds in combination, and to use one of the above-mentioned ones, which are preferably 'the following formula (IV) or the following group of phthalic acid compounds, and the aromatics represented by the following formulas (R9) (R6) N2

(COOH) m (m) (wherein nl represents any of 1 to 4, n2 represents an integer of J53278.doc -15-201139358 in '4; Re represents a C1~C6 alkyl group, a nitro group or a hydroxyl group) [ (10) (R7) m2 (COOH) ml (N) (wherein ml represents any integer of 1 to 4; m2 represents any integer of 0 to 2; R? represents C1 to C6 alkyl, nitrate a base, a hydroxyl group or a group represented by the following formula, [Chem. 11]

(COOH)q (wherein 'q represents an integer of 1 or 2; * denotes a bonding position)). 6 C7~C6 alkyl group of R7 includes a cycloalkyl group, and specifically, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a second butyl group, and a second group are mentioned. Base, cyclobutyl, cyclopropylmethyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, oxime-ethyl, n-hexyl, isohexyl, 4·methylpentyl , 3-mercaptopentyl, 2·methylpentyl, i•methylpentyl, 3,3-dimethylbutyl, 2,2·dimethylbutyl, and the like. In the soil == formula (ΙΠ), it is preferably an aromatic acid retardation represented by the following formula (1) [Chemical 12] 153278.doc 201139358

COOH

In the formula, R! represents a C1 to C6 alkyl group, a C1 to C6 alkoxy group or a hydroxyl group. The C1-C6 alkyl group is preferably a C1-C4 alkyl group, and may have a substituent. The C1-C6 alkyl group includes a cycloalkyl group, and specific examples thereof include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a second butyl group, and a third butyl group. Cyclobutyl, cyclopropylmethyl, n-pentyl, isopentyl, 2, nonylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, isohexyl, 4·methylpentyl, 3 -decylpentyl, 2-methylpentyl, 1-decylpentyl, 3,3-dimercaptobutyl, 2,2-dimercaptobutyl, 1,1-didecylbutyl, 1,2-dimethylbutyl, 1,3-dimercaptobutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, and the like. The C1-C6 alkoxy group is preferably a C-C4 alkoxy group, and may have a substituent. Specific examples of the C1 to C6 alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. , n-pentyloxy, isopentyloxy, 2-hydrinobutoxy, 1-ethylpropoxy, 2-ethylpropoxy, neopentyloxy, n-hexyloxy, 4-decylpentane Oxyl, 3-mercaptopentyloxy, 2-methylpentyloxy, 3,3-dimercaptobutoxy, 2,2-dimercaptobutoxy, ι,ι-didecyloxy Base, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy and the like. (Imidazole compound) The imidazole compound used in the present invention is a compound represented by the following formula (11): 153278.doc • 17-201139358 ° sitting compound and β-mirryl compound. [Chem. 13]

Ν, (Π) Ν

• R2 specifically contains a structure of the following formula (II). [Chem. 14]

Wherein 'R_2 represents a hydrogen atom, a Cl~C10 alkyl group or a cyanoethyl group, preferably a hydrogen atom. The aryl group or the arylalkyl group may be a C1 to C10 alkyl group, preferably a C1 to C6 alkyl group, and f 1 may have a substituent. Specific examples of the C1 to C10 alkyl group include methyl group, hexyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, isobutyl group, dibutyl butyl group, n-pentyl group, n-hexyl group and fluorene. Base, isoindolyl, thiol and the like. An aryl group means a monocyclic or polycyclic aryl group. Here, in the case of a polycyclic aryl group, in addition to the completely unsaturated group, #includes a partially saturated group. For example, a phenyl group, a decyl group, a fluorenyl group, a benzyl group, a bis group, a tetrazinc group or the like can be given. In the #, a C6 to C10 aryl group is preferred. Further, the aryl group may have a substituent. The arylalkyl group is a group in which the above aryl group is bonded to an alkyl group, and is exemplified by benzyl 153278. Doc 201139358, phenethyl, 3-phenyl-n-propyl, fluorenyl-phenyl-n-hexyl, naphthylmethylnaphthylethyl, naphthalen-2-yl-n-propyl, 茚_1_yl fluorenyl and the like. Among these, a C6 to C10 aryl C1 to C6 alkyl group is preferred. Further, the arylalkyl group may have a substituent. R3 to R5 each independently represent a hydrogen atom, a nitro group, a halogen atom, a CN20 alkyl group, a C1 to C20 alkyl group substituted by a hydroxyl group, an aryl group, an arylalkyl group or a fluorenyl group of C1 to C20. Examples of the C1 to C20 alkyl group include a methyl group, an ethyl group, a n-propyl isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, an n-hexyl group, and a decyl group. The hydrazine, isodecyl, fluorenyl, lauryl, +tridecyl, myristyl, pentadecyl, palmitoyl, heptadecyl, stearyl or the like is preferably a C1 to C10 alkyl group. Examples of the aryl group and the arylalkyl group include the same groups as the base of the ruler 2. The CK20 brewing group refers to a group in which a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group is bonded to a carbonyl group. Examples of the sulfhydryl group include a fluorenyl group; an acetamyl group, a propyl fluorenyl group, a butyl fluorenyl group, a pentyl group, a hexyl group, a heptyl group, a octyl group, an anthracenyl group, a fluorenyl group, and a thiol group. ,8-fluorenyl aryl, 3-ethyloctyl, 3,7-dimethyloctyl, deca-decyl, dodecylfluorenyl, tridecyldecyl, tetradecanedecyl, ten Five-burning base, fifteen-burning sulfhydryl, L-methylpentadecyl (tetra)yl, 14-methylpentadecanoyl, 13,13-didecyltetradecanedecyl, heptadecane, 15_ An alkylcarbonyl group such as methylhexadecane, octadecane, i-methylheptadecane, nonadecane, eicosyl and eicosyl; propylene fluorenyl , methyl propyl sulphate, allylic fluorenyl, cinnabar thiol (four) base silk; B quick base 153278. Doc -19- 201139358 alkynylcarbonyl such as benzyl or propylcarbonyl; arylcarbonyl such as benzamyl, naphthylcarbonyl, biphenylyl, fluorenylcarbonyl; 2_πpyridylcarbonyl, thienyl Isoheteroarylcarbonyl and the like. Among these, a Cl~C2〇(carbonyl group-containing) fluorenyl group is preferred, and a C1~C6 fluorenyl group is particularly preferred. Specifically, 'is the microphone represented by the formula (Π). The compound can be exemplified by imidazole, 2-ethyl-4-methylimidazole, 2-mercaptoimidazole, jbenzyl-2-indoleimidazole, 2-heptadecylimidazole, 2-undecylimidazole , 2_phenyl_4_methyl_5_ hydroxydecyl imidazole '2-phenylimidazole, 2·styl _4-methylimidazole, 1-benzyl phenyl-2-phenylimidazole, 1,2-di Mercaptoimidazole, cyanoethyl 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, hydrazine-cyanoethyl-2-undecylimidazole, 1- Cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxydecyl imidazole, etc., preferably 2-ethyl-4-methylimidazole, 2-methylimidazole, hydrazine-benzyl Base 2·methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 2-phenyl-7-nonyl-5-hydroxymethylimidazole, 2-phenylimidazole or 2-phenylene Base _4,5-dihydroxymethyl mouth rice. sit. The imidazoline compound represented by the formula (II) may, for example, be 2 fluorenyl 2-phenyl imi (tetra), 2 • decyl (tetra) lin, 2 hexadecane oxazoline, 2-ethyl mum. Sitting porphyrin, 2_isopropyl hydrazine. The porphyrin, the 2, the diterpene-based saliva, the 2-phenyl-4-methylsulfate, and the like are preferably 2 methylimine. Sitting on the Lin or 2_ stupid base. (Carboxylic acid compound simazole compound eve).  1 of the alpha.  (Manufacturing method of the inclusion compound or the composition thereof) The inclusion ratio of the carboxylic acid compound and the acetophenone compound which is substantially 丄: 2 or the composition thereof can be obtained by the following method or the like. 153278. Doc 8 •20· 201139358 (1) Method of adding an alcohol solution of a carboxylic acid compound to a succulent compound (7) Method of adding a few acid compound to an alcohol solution of a medicinal compound The following describes the details of the method (1). An alcohol solution of a carboxylic acid compound is added to the imidazole compound while stirring is carried out as needed. The addition of the alcohol solution of the m acid compound is carried out and is usually added continuously or in divided portions for 5 to 120 minutes. ‘,,, after the addition of the alcohol solution of the carboxylic acid compound, it is allowed to stand at room temperature for 0 to 5 hours, and is heated at room temperature to 4 Torr for 5 hours or heated to reflux. The ratio of the ratio of the acid compound to the oxime compound is preferably 1 Torr to 5 hrs relative to the slow acid compound (host), and more preferably 0. 5~3. 0 mole. The alcohol solvent is exemplified by a lower alcohol such as decyl alcohol, ethanol or n-propanol, and more preferably methanol. The amount used is usually 0% by weight relative to the carboxylic acid compound. 5 to 50 times the amount. ^ The step after the heat treatment or the heat reflux treatment may be carried out, for example, by simply stopping the heating or heating the reflux treatment, preferably by heating and then leaving it at room temperature for one night. After the solid compound is precipitated, the target compound is obtained, for example, by filtration drying. The details of the method of (2) are explained below. After the imidazole compound is suspended or dissolved in an alcohol (the alcohol suspension and the alcohol solution are referred to as an alcohol solution), the carboxylic acid compound is added while stirring as necessary. The addition of the carboxylic acid compound is not particularly limited, and it is usually added continuously or in divided portions at 5 to 12 Torr. 153278. Doc -21 - 201139358 After the addition of the carboxylic acid compound, it is allowed to stand at room temperature for 0 to 5 hours at room temperature to 40 °C. (: heating under 〇~5 hours or heating under reflux for ~5 hours. As a compounding ratio of the acid-lowering compound and the imidazole compound, the imidazole compound (guest) is preferably 〇丨~ relative to the diacid compound (main body) 1 mol. 5 〇莫耳' is better for 0. 5~3. 0 mole. The alcohol solvent may, for example, be a lower alcohol such as methanol, ethanol or n-propanol, and more preferably methanol. Use $ is usually 0% by weight relative to the acid-producing compound. 5 to 50 times the amount. For reference, a method for producing an inclusion compound of HIPA and 2p4MHZ with a molar ratio of i: i is described below. (Manufacturing method of the HIPA and 2P4MHZ molar ratio i: the inclusion compound of 丄) The molar ratio of HIPA to 2P4MHZ is substantially only 丨: i. The inclusion compound can be obtained by the following method or the like. After dissolving the HIPA in the alcohol, add (4) as needed, and add 2P4MHZ. The addition of 2P4MHZ is not particularly limited and is usually carried out continuously for 5 minutes or more, preferably 5 minutes to 12 minutes. After adding 2P4MHZ, it is left to stand at room temperature for ～5 hours, and heated at room temperature ~40 ° C for ～5 hours or heated to reflux for ～5 hours. As 1 .  The ratio of the preparation method of the inclusion compound to the compounding ratio is preferably 0. The relative value of the HIPA (host) is 2, and the 2P4MHZ (guest) is preferably 0. 1~5. 0 mole, more preferably 0. 5~3. 0 mole. As 1 .  The alcohol solvent of the method for producing a packaged compound may, for example, be a lower alcohol such as methanol, ethanol or n-propanol, preferably methanol. The amount used is usually 153278. Doc 2 8 201139358 For HIPA it is 〇 5~5〇. The step of treating, or heating, the refluxing treatment may, for example, be carried out by simply stopping: heat or heat reflux treatment to precipitate a solid compound, preferably by heating to a temperature-night. After the solid compound is precipitated, the target compound is obtained, for example, by filtration drying.曰 (curable epoxy resin composition) The inclusion compound of the present invention or a composition thereof can be used as an epoxy resin hardener or a hardening accelerator, mixed with an epoxy resin, for example, used as a semiconductor encapsulant 0 for use as a semiconductor seal The cured epoxy resin composition such as an agent contains an epoxy resin, an inclusion compound of the present invention, and other additives as needed. As the epoxy resin, the epoxy resin may be any of various previously known polyepoxy compounds, and examples thereof include bis(4-hydroxyphenyl)propane diglycidyl ether and bis(4_hydroxy 3'5 — > Benji), propylene, monoglycidyl hydrazine, bis(4-aminobenzopyrene), ethylene diglycidyl ether, bis(4.hydroxyphenyl)methane diglycidyl ether, isophthalic diglycidyl ether, Pyrogallol triglycidyl ether, trisylbiphenyl triglycidyl ether, tetraglycidyl dibenzophenone, bis-diphenol diglycidyl ether, tetradecyl bisphenol quinone diglycidyl ether, double Cc diglycidyl ether, bisphenol hexafluoropropane diglycidyl ether, 13•bis "^2,3-epoxypropionyl)-1-trifluoromethyl-2,2,2-trifluoro Ethyl] stupid, 1,4_bis[1_(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl] stupid, 4,4,_ An aromatic glycidyl ether compound such as bis(2,3_epoxypropoxy)octafluorobiphenyl or a phenol novolac type diepoxide; alicyclic diepoxy condensation, ring 153278. Doc •23· 201139358 Group of epoxidized adipate, alicyclic diepoxy sulphuric acid vinegar, oxidized ethoxylated cyclohexyl epoxide, etc.; diglycidyl phthalate , diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethyl glycerol phthalate, hexafluorophthalic acid dimethylglycolic vinegar, a glycerol vinegar compound such as benzoic acid diglycidyl vinegar, cyclopentanol glycidol 6, dimer acid glycidol vinegar, diglycidyl aniline, diglycidyl toluidine, triglycidyl amide benzene, four Glycidyl group: glycidylamine compound such as aminodiphenylmethane or diglycidyl tris-aniline; diglycidylacetamidine, glycidyl glycidyloxyalkylene urea, isocyanide A heterocyclic epoxy compound such as uric acid triglycidyl ester. Further, examples of the liquid epoxy resin include polyalkylene groups such as (poly)ethylene glycol diglycidyl hydrazide, (poly)propylene glycol diglycidyl _, trimethyl methacrylate & triglycidyl ether; Ether type epoxy compound; dimer acid diglycidyl S 曰, phthalic acid diglycidyl phthalate, tetrahydrophthalic acid diglycidyl vinegar and other glycidol vinegar type epoxy compound; (meth) acrylic acid The glycidol is a monopolymer such as cilexetil glycidyl ether or a copolymer of the monomer and other soft unsaturated monomers. The term "soft unsaturated monomer" means that the glass transition temperature of the homopolymer is less than 6 〇〇c, and examples thereof include acryl 7 , propylene ( 4 ) s s, and (meth) succinate butyl 8 ( Isobutyl methacrylate, 2-ethylhexyl (meth) acrylate, lauryl methacrylate, and the like. 2) Inorganic filler The epoxy resin composition of the present invention may contain the above-mentioned inclusion compound and epoxy resin, or may contain no 153278 in addition to the inclusion compound and epoxy resin. Doc 8 •24- 201139358 Machine-filled epoxy resin composition as inorganic filler, no glass, 蕤a + η: # n艮, for example, quartz glass is obtained by flame melting.球形 等 等 所 球形 球形 、 、 、 、 球形 球形 球形 球形 球形 球形 IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT IT These may be used alone or in combination of two or more. 3) A hardener or an effect accelerator as a hardener which can be contained in the epoxy resin composition of the present invention, as long as 2 can react with the epoxy group of the epoxy resin to harden the epoxy resin. In the same manner, the curing accelerator which can be contained in the epoxy resin group of the present invention is not particularly limited as long as it is a substance which promotes the above-mentioned curing reaction. As such a curing agent or a curing accelerator, any of those conventionally used as a curing agent or a curing accelerator for an epoxy resin may be used. For example, an amine compound such as an aliphatic amine, an alicyclic type or a heterocyclic type, a scented amine, a modified amine, or the like; a oxazole compound, an imidazoline compound, and a guanamine compound; , an ester compound, a phenol compound, an alcohol compound, a thiol compound, a (4) compound, a thioether compound, a I compound, a thiourea compound, a Lewis system: a dish, a dish compound, an acid needle system A compound, a phosphonium salt compound, an active Shihe compound, an aluminum complex, or the like. Specific examples of the curing agent or the curing accelerator include compounds. 153278. Doc -25· 201139358 Examples of the aliphatic amines include ethylenediamine, u-propylenediamine, diethylenediamine, Μ_taudiol, 16 hexanediamine, diethylenetriaminetriethylenetetraminetetraethylene Amine, monopropylene diamine, dimethylaminopropylamine, diethylaminopropylamine dimethyl hydrazine, 6. Hexamethylenediamine, pentanediamine, bis(2-dimethylaminoethyl), pentadecyl-ethylenediamine, tertiary triamine, 1,4-diazabicyclo (2,2,2 ) Xin Shao (triethylenediamine), ν, ν, ν,, ν. _ tetramethyl. ΜHexane diamine, team N'N,, y tetramethyl propylene diamine, ν, ν, ν, bound tetramethylethylenediamine, hydrazine, hydrazine _ methyl hexylamine, monobutylaminopropylamine, two Methylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, and the like. Examples of the cyclized and heterocyclic amines include κ " sputum, thin hesandiamine', isophor, diamine, methyl morpholine, ethyl morpholine, hydrazine, hydrazine, hydrazine -Tris(dimethylaminopropyl)hexahydrogenate, 3,9-bis(3_aminopropene) 2'4,8,1〇-tetraoxaspiro (5,5)_| _ mono-alcohol adduct, N-aminoethyl bottom well monomethylaminoethyl peptide 11 well, bis(4-aminocyclohexyl)methane, hydrazine, Ν'-dimercaptopurine well, dinitrogen Heterobicyclo[4. 5. 0] undecene _7 and the like. Examples of the aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenyl decane, diaminodiphenyl hydrazide, benzyl decylamine, and dimethyl Alkylbenzylamine, m-xylylenediamine, pyridine, picoline, α-mercaptobenzylmethylamine, and the like. Examples of the modified amines include epoxy compound addition polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polymoon, ketone-terminated polyamine, dicyandiamide, Anthracene, an organic acid hydrazine, a diamine maleimonitrile, an amine sulfimine, a boron trifluoride-piperidine complex, a boron trifluoride-monoethylamine complex, and the like. 153278. Doc -26· 201139358 Examples of the imidazole-based compound include imidazole, indole imidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, and ethylidazole, 2-ethyl Imidazole, 3-ethylimidazole, phenethylimidazole, 5-ethylimidazole, bupropionimidazole, 2-n-propylimidazole, hydrazine-isopropylimidazole, 2-isopropylimidazole, 1-n-butyl Imidazole, 2-n-butylimidazole, hydrazine isobutylimidazole, 2-isobutylimidazole, 2-deca-alkyl-1H-imidazole, 2-peptadecyl-m-imidazole, i,2- Dimethyl oxazole, dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-mercaptoimidazole, · Stupid imidazole, 2·phenyl•imidazole, 4-methyl-2-phenyl-mu 2_phenyl·4·methylmeridene, i•pyrylene_2_methylΜ, ^1 1 stupid Basic taste „sit, κ-nitroethyl-2-methyl taste. Sit, 1-cyanoethyl-2-ethyl_4·nonyl imidazole, acetophenethyl 2-_undecyl Spit, i-cyanoethyl-2_stupyl oxime, 2_phenylimidyl isocyanurate adduct, 2-methylimidazole-isocyano cyanide adduct, 2·phenyl _ 4,5-di-dimethylmethyl hydrazine, 2. Stupid base|methyl_5_minus methyl w, cyanoethyl-2-phenyl·4,5·di(2, cyanoethoxy)methyl meth.圭, i•12 院基·2·Methyl m gasification, mow, phenyl, and pyridine. As the (four) compound, for example, 2 A (tetra) can be mentioned. Sitting on the Lin, 2_ phenyl ° meters, sitting on the Lin and so on. The polyamine compound obtained by the condensation of a dimer acid and a polyamine can be mentioned as a brewable amine compound. v The compound 'is, for example, a living carbonyl compound such as an acid-lowering aryl group or a thioaryl group. As a compound, an alcohol compound, a thiol compound, a mystery 153278. Doc • 27.  201139358 Compounds and thioether compounds, for example, as a phenol resin hardener, can be enumerated. An aralkyl type phenol resin such as a phenol aryl group-based resin or a naphthol aralkyl resin; a novolac type phenol resin such as a phenol novolak resin or a cresol novolac resin, or a modified resin such as epoxy group or Butylated phenol novolak type phenol resin, dicyclopentadiene modified phenol resin, p-xylene modified phenol resin, triphenol alkane type phenol resin, polyfunctional phenol resin, and the like. Further, a polyol, a polythiol, a polysulfide, 2_(dimethylaminomethylphenol), 2,4,6-tris(dimethylaminomethyl)phenol, 2,4,6_three Tris(2-ethylhexyl) hydrochloride of (dimethylaminomethyl)phenol or the like. Examples of the gland-based compound, the sulfur-based compound, and the Lewis-based compound include a butylated pulse, a butylated melamine, a butylated sulfur gland, a trifluorinated side, etc., and an organic phosphine compound and a butyl group. An alkylphosphine such as a phosphine such as a phosphine such as a phenylphosphine; a dimethylphosphine, a diphosphine or the like: a secondary phosphine such as an alkylphosphine, a diphenylphosphine or a methylethylphosphine; and a trisphosphine monoethylphosphine And a tertiary phosphine such as triphenylphosphine. The acid anhydride-based compound may, for example, be phthalic anhydride, tetra-formic anhydride, hexahydro-o-phthalic anhydride, or acetaminophen. #风耶本-甲肝,甲其酸野, 内亚Methyltetrahydrophthalene methylene-2 endomethylene tetrachaophthalic acid anhydride, cis-butanoic acid liver, anhydride,:-butene monophthalic anhydride, trimellitic anhydride, chloric anhydride, tetras-tetraene Succinic anhydride, benzophenone tetracarboxylic anhydride (trimellitic acid vinegar), glycerol (trimellitic anhydride vinegar:: slow acidity, polysebacic anhydride, etc. methylcyclohexane 153278. Doc 8 •28· 201139358 Also as an iron salt compound, and active compound _ Shao complex, = can be listed. Aryl diazonium salt, diaryl sulfonium salt, triaryl sulfonium salt, triphenyl decyl alcohol-aluminum complex, triphenyl methoxy decane aluminum complex, peroxidation , _ — w ^ two bases > 6 kiln alcohol - three (salty sulphate) I ru complex and so on. As the above-mentioned curing agent or curing accelerator, it is particularly preferable to use an amine compound "myrazine compound or a benzophenone compound. Among the benzene 1 compounds, a phenol resin curing agent is more preferably used. 4) Other Additives In the epoxy resin composition of the present invention, in addition to the above, a plasticizer, an organic solvent, a reactive diluent, an extender, a filler, a reinforcing agent, a pigment, and a flame retardant may be blended as needed. Various additives such as a chemical agent, a thickener and a release agent. As other additives, vinyl trimethoxy decane, vinyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, γ _ mercapto propylene methoxy propyl dimethoxy zeoxime, γ-methyl propylene methoxy propyl triethoxy decane, γ-aminopropyl trimethoxy decane, γ · aminopropyl three Ethoxy oxime, Ν-β-(aminoethyl)-γ-aminopropyltrimethoxy zeoxime, Ν_β_(aminoethyl)-γ-aminopropyltriethoxy decane, hydrazine _Phenyl-γ-aminopropyltrimethoxy sulphur, Ν-phenyl-γ-aminopropyltriethoxy sulphur, 丫-s-propyltrimethoxy decane, γ-sulfanyl a decane coupling agent such as propyl triethoxy decane; calcium hydrogencarbonate, light calcium carbonate, natural cerium oxide, synthetic cerium oxide, molten cerium oxide, kaolin, clay, titanium oxide, barium sulfate, zinc oxide,虱 铭 、, magnesium hydroxide, talc, mica, crushed stone, titanic acid 153278. Doc •29- 201139358 Potassium, aluminum borate, sepiolite, hard calcite, etc.; nbr, polybutadiene, chloroprene rubber, polyfluorene oxide, crosslinked NBR, crosslinked BR, acrylic, Core-shell acrylic, urethane rubber, polyester elastomer, functional NBR containing liquid, liquid polybutadiene, liquid polyester, liquid polysulfide, modified polyoxyl , an elastomer modifier such as a urethane prepolymer; hexabromocyclodecane, bis(dibromopropyl)tetrabromobisphenol A, isocyanuric acid tris(di-propyl) ester, phosphoric acid tri Tribromoneopentyl)ester, decabromodiphenyl oxide, bis(pentabromophenyl)ethane, tris(tribromophenoxy)trimium, and exoethyl bis(tetrabromoophthalene) Amine), polybromophenyl decane, brominated polystyrene, tetrabromobis-A polycarbonate, bromobenzene oxirane, poly(pentabromobenzyl acrylate), triphenyl phosphate, tridecyl phenyl phosphate, Tris(dimethylphenyl) phosphate, toluene diphenyl phosphate, diphenylene diphenyl phosphate, bismuth (2,6-xylene) phosphate, 2-ethylhexyl diphenyl phosphate, isophthalic acid Diphenol double Phenyl phosphate vinegar), Bishuang A bis (diphenyl phosphate), bisphenol a bis (diphenyl phenyl phosphate), resorcinol bis (di-2,6-diphenyl phenyl phosphate) , tris(gas ethyl) vinegar, tris(cyclopropyl) phosphate, tris(dichloropropyl) phosphate, tris(tribromopropyl) phosphate, diethyl-N,N-double (2 Hydroxyethyl)aminomercaptophosphonate, anionic oxalic acid treated aluminum hydroxide, nitrate treated aluminum hydroxide, high temperature hot water treated aluminum hydroxide, stannic acid surface treated hydration Metal compound, magnesium hydroxide surface treated with nickel compound, oxidized town surface treated with polyoxopolymer, pr〇c〇bite, multi-surface treated hydrated metal compound, cationic polymer treated hydroxide Flame retardant such as magnesium; high density polyethylene, polypropylene, polystyrene, polydecyl propylene 153278. Doc 201139358 Dilute acid brewing, polyethylene, nylon 6,6, poly_, poly_, polyphosphonium imide, polybutylene terephthalate, poly La, polycarbonate, concrete and other engineering plastics Plasticizer; n-butyl glycidol, phenyl glycidyl ether, styrene oxide, tert-butylphenyl glycidyl ether, dicyclopentane: diepoxide, phenol, cresol, third Diluents such as phenol; extenders; enhancers; colorants; thickeners; higher fatty acids, higher fatty acid vinegar, higher fatty acid calcium, etc., such as carnauba wax or polyethylene wax and other release agents. The blending amount of the additives is not particularly limited, and the blending amount can be appropriately determined within the limits of obtaining the effects of the present invention. Further, the epoxy resin composition of the present invention may contain other resins in addition to the epoxy resin. Examples of the other resin include a poly-resin resin, an acrylic resin, a fluorene-based resin, and a polyurethane resin. 5) Preparation of epoxy resin composition and cured product thereof The ratio of the epoxy resin to the inclusion compound of the present invention or a combination thereof is 'with respect to the epoxy group of the epoxy resin, 1 mole, and the compound 戍The content of the imidazole compound in the composition is preferably 〇〇ι~ι〇 molar is preferably 0·1~i. 0 mole, more preferably 0. 3~1. 0 mole. Further, the epoxy resin is formed into a combination (4) by mixing an epoxy resin with the inclusion compound of the present invention or a composition thereof, but in order to form a charge-mixed state, it is usually 60 to just. Heating at a temperature of about C is mixed. Two: In the manufacture of an epoxy hardening resin, the single liquid at the temperature at this time is stable. The epoxy resin composition produced may be either solid or liquid. And h as a curing method for the epoxy resin forming composition, as long as it is heated 153278. Doc -31 · 201139358 The method of curing the composition for forming an epoxy resin is not particularly limited, and the heating temperature for the heat treatment is usually 60 to 250 °C. EXAMPLES Hereinafter, examples will be described, but the technical scope of the present invention is not limited to the examples. Further, in the following examples, iNMR was carried out by using DMSO-d6 or MeOH-d4 as a measurement solvent and measuring at 25 °C. 1 Preparation of the inclusion compound [Synthesis Example 1] 2P4MHZ was added to the flask. 67 g (109. After 8 mmol), while stirring, add HIPA 20 g (l 09. 8 mmol) half of the liquid obtained by dissolving in 170 ml of sterol. Wash with 11 mL of methanol and place at room temperature. After 5 hours, while stirring, the remaining HIPA methanol solution was added, washed with 11 mL of methanol, and placed at room temperature for 0. After 5 hours, it was heated to reflux for 3 hours. Thereafter, after standing at room temperature for one night, it was filtered and vacuum dried to obtain a product 28. 89 g (yield 71%). The product obtained was analyzed by 1H NMR, X-ray diffraction and thermal analysis (DSC), and as a result, the product was HIPA: 2P4MHZ was a crystal of the inclusion compound of 1:2. Further, the purity of the 1:2 inclusion compound was 91%. A thermal analysis (DSC) chart of the temperature change of the obtained inclusion compound is shown in Fig. 1. [Synthesis Example 2] 2P4MHZ was added to the flask. 67 g (109. 8 mmol) and sterol 130 ml and mixed in the alcohol solution, while stirring, add HIPA 10 g in 20 minutes (54. 9 mmol). Place at room temperature 0. After 5 hours, add 153278. Doc -32· 8 201139358 Heat reflux for 3 hours. Then, after standing at room temperature for one night, it was filtered and vacuum dried, thereby obtaining a product 29. 91 g (yield 97. 5%). The product obtained was analyzed by WNMR, X-ray diffraction and thermal analysis (DSC), and as a result, the product was HIPA: 2P4MHZ was a crystal of a 1:2 inclusion compound. Further, the purity of the 1:2 inclusion compound was 97%. The thermal analysis (DSC) chart and the iNMR chart of the temperature change of the obtained inclusion compound are shown in Fig. 2-1 and Fig. 2-2. [Synthesis Example 3] 2P4MHZ was added to the flask. 67 g (109. After 8 mmol), while stirring, add HIPA 10 g in 15 minutes (54. 9 mmol) liquid obtained by dissolving in 130 ml of methanol. Place at room temperature 0. After 5 hours, the mixture was heated under reflux for 3 hours. Thereafter, after standing at room temperature for one night, it was filtered and vacuum dried to obtain a product 29. 74 g (yield 97%). The obtained product was analyzed by hNMR, X-ray diffraction and thermal analysis (DSC), and as a result, the product was HIPA: 2P4MHZ was a crystal of a 1:2 inclusion compound. Further, the purity of the 1:2 inclusion compound was 99%. The thermal analysis (DSC) chart and the ]HNMR chart of the temperature change of the obtained inclusion compound are shown in Figs. 3-1 and 3-2. [Synthesis Example 4] Except that an unsubstituted mic 0 (hereinafter referred to as Im) was used. 48 g (109. 8 mmol) In the same manner as in Synthesis Example 2 except for 2P4MHZ, an inclusion compound having HIPA: Im of 1:2 was obtained. Further, the purity of the 1:2 inclusion compound was 77%. The thermal analysis (DSC) chart and the iNMR chart of the temperature change of the obtained inclusion compound are shown in Fig. 4-1 and Fig. 4-2. 153278. Doc -33- 201139358 [Synthesis Reference Example 1] (1: Preparation of inclusion compound) HIPA 20 g was introduced into the flask (109. 8 mmol) and 126 ml of methanol were mixed and mixed to obtain 2P4MHZ in 15 minutes while stirring. 67 g (109. 8 mmol). After standing at room temperature for 2 hours, it was heated to reflux for 3 hours. Then, after standing at room temperature for one night, it was filtered and vacuum dried, thereby obtaining a product 39. 56 g (yield 97. 3%). The product obtained was analyzed by 'HNMR, X-ray diffraction and thermal analysis (DSC), and as a result, the product was HIPA: 2P4MHZ was a 1:1 crystal of the inclusion compound. Further, the purity of the 1:2 inclusion compound was 0%. A thermal analysis (DSC) chart of the temperature change of the obtained inclusion compound is shown in Fig. 5. [Synthesis Reference Example 2] Except for using lm 7. 48 g (109. In the same manner as in the synthesis of Reference Example 1, except that 2P4MHZ was used, an inclusion compound having a HIPA: Im of 1:1 was obtained. [Synthesis Comparative Example 1] (Preparation of a mixture of 1:1 and 1:2 inclusion compound) HIPA was introduced into a flask 36. 43 g (200 mmol), 2P4MHZ 37. 65 g (200 mmol) and 230 ml of sterol were mixed and heated under reflux for 3 hours. Then, after standing at room temperature for one night, it was filtered and vacuum dried, thereby obtaining a product 64. 41 g (yield 87. 2%). The obtained product was analyzed by 1H NMR, X-ray diffraction, and thermal analysis (DSC), and as a result, the product showed data different from those of Examples 1 and 2, and thus it was judged that it was HIPA: 2P4MHZ was a 1:1 package. A crystal obtained by mixing a compound with a 1:2 inclusion compound. Further, the purity of the 1:2 inclusion compound was 18%. A thermal analysis (DSC) chart of the temperature change of the obtained inclusion compound is shown in Fig. 6. 2 Manufacture of epoxy resin composition 153278. Doc -34- 8 201139358 Manufacture of 2-1 biphenyl type epoxy resin composition [Composition reference example 1] will be converted to 0 by imidazole. The inclusion compound obtained in the method of the synthesis of 249 g, YX4〇〇〇h (manufactured by Mitsubishi Chemical Corporation) as a conjugated epoxy resin. 445 g, to wax (registered trademark) 131 (manufactured by East Asia Chemical Co., Ltd.) 249 249 g as a release agent, FB-940 spherical cerium oxide (manufactured by Electric Chemical Industry Co., Ltd.) as a filler 179. 97 g, LS294 as a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) 0. 383 g, novolac phenol as a hardener PSM-426! OH equivalent 103 (manufactured by Qunrong Chemical Industry Co., Ltd.) 6. 701 g was heated and kneaded at 10 ° C for 5 minutes. After cooling, the mixture was pulverized to produce a biphenyl type epoxy resin composition. [Composition Example 1] A biphenyl type was produced in the same manner as in Reference Example 1, except that the inclusion compound obtained in the method of Synthesis Example i was used instead of the inclusion compound obtained in the method of Synthesis Reference Example 1. Epoxy resin composition. 2-2 Neighbors are made of varnish-type epoxy resin composition [Composition Reference Example 2] will be converted to 0. 378 g of the conjugated mouth obtained in the method of the reference example k, as the o-cresol novolac epoxy resin (10) (3) · 55 ethoxylate § 191~2〇1 (manufactured by Nippon Kayaku Co., Ltd.) 18. 886 g, TOWAX (registered trademark) 13U as a release agent, manufactured by East Asia Chemical Co., Ltd.) G. 378 g, FB-940 spherical dioxin (manufactured by Electric Chemical Industry Co., Ltd.) 169 97 g as a filler, as 153278. Doc •35- 201139358 LS-2940 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0 944 g of decane coupling agent, novolac phenol PSM_4261 OH equivalent as a hardener 1〇3 (manufactured by Qunrong Chemical Industry Co., Ltd.) 9. 443 g was heated and kneaded under a loot for 5 minutes, cooled and then pulverized to produce a biphenyl type epoxy resin composition. [Composition Example 2] O-cresol was produced in the same manner as in Reference Example 2, except that the inclusion compound obtained in the method of Synthesis Example 1 was used instead of the inclusion compound obtained in the method of Synthesis Reference Example 1. A novolac type epoxy resin composition. Manufacture of 2-3 liquid epoxy resin composition [Composition Reference Example 3] The inclusion compound obtained in the method of Synthesis Reference Example 1 in terms of imidazole was converted to 0.4 g, as a liquid epoxy resin. Epotohto YD-128 (manufactured by Tohto Kasei Co., Ltd.) 10 g of 'mixed' to produce a liquid epoxy resin composition. [Composition Example 3] A liquid ring was produced in the same manner as in Reference Example 3, except that the inclusion compound obtained in the method of Synthesis Example 1 was used instead of the inclusion compound obtained in the method of Synthesis Reference Example 1. Oxygen resin composition. [Composition Example 4] A liquid ring was produced in the same manner as in Reference Example 3, except that the inclusion compound obtained in the method of Synthesis Example 4 was used instead of the inclusion compound obtained in the method of Synthesis Reference Example 1. Oxygen resin composition. [Composition Reference Example 4] 153278. Doc-36- 8 201139358 A liquid epoxy was produced in the same manner as in Reference Example 3, except that the inclusion compound obtained in the method of Synthesis Reference Example 2 was used instead of the inclusion compound obtained in the method of Synthesis Reference Example 1. Resin composition. [Test Example 1] (Spiral flow test) The epoxy resin compositions obtained in the compositions of Examples 1 and 2, and the methods of Reference Examples 2 and 2, respectively, were tableted and molded into tablets. These tablets were injection molded for 3 minutes under the conditions of 17 passages and a pressure of 7 〇 KgfW using an Archimedes screw mold and a transfer molding machine, and the length of the produced product was measured. The spiral (four) value is the initial value and 25. The value of the mouth is ... after the day, the equivalent value is shown in the first table. In the spiral flow test, the larger the value, the better the fluidity. [Test Example 2] (gelation time) ^ ^ ^ & preliminary application examples 3 and 4 'combination 4, the epoxy resin composition obtained by the household is placed at 175t and the self-owned (four) knife is set The adhesion to the sample is eliminated: the time when the hot plate is removed or the time when the adhesion disappears. When the gelation time of the result j is set to the time of stable stability, when the heat-sealing material is hard-sealed, the faster the solidification is reached, the faster the solidification is, the lower the gelation time is, and the shorter the gelation time is. For the gelation time is short (storage stability) and especially for the case of liquid epoxy resin, compared to J5327S. Doc •37· 201139358 The epoxy resin compositions obtained in the methods of the compositions of Examples 3 and 4 and the composition of Reference Example 3 were stored at 30 ° C and visually observed, and the measurement was terminated at the time of curing, Storage stability was evaluated. The results are shown in the second table. [Table 1] Table 1 Epoxy Resin Composition Spiral Flow Initial Value (cm) 25° 〇 7 days later (cm) Composition Reference Example 1 117. 05 105. 67 Composition Example 1 192. 18 130. 08 Composition Reference Example 2 164. 13 145. 22 Composition Example 2 174. 65 161. 68 [Table 2] Table 2 Epoxy Resin Composition Gelation Time (sec) Preservation Stability Composition Reference Example 3 226 Curing Composition between 58 and 89 Days Reference Example 4 57 Between 21 and 25 days Cured Composition Example 3 204 100-day or more uncured composition Example 4 44 Curing industrial property between 15 and 21 days According to the present invention, an aromatic carboxylic acid compound and an imidazole compound can be obtained in high purity. '· 2 packaged compound. Further, in the present invention, since the 1:2 inclusion compound is successfully produced in high purity, it is possible to manufacture either a 1:1 inclusion compound and a 1:2 inclusion compound as a hardener or hardening. A curable epoxy resin composition of a promoter and a cured product thereof. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a thermal analysis (DSC) chart of temperature change of the inclusion compound obtained in Synthesis Example 1. 153278. Doc-38 - 8 201139358 Fig. 2-1 is a diagram showing a thermal analysis (DSC) chart of the temperature change of the inclusion compound obtained in Synthesis Example 2. 2-2 is a view showing a 1H-NMR chart of the inclusion compound obtained in Synthesis Example 2. Figure 3-1 is a graph showing the temperature of the inclusion compound obtained in Synthesis Example 3, and the thermal analysis (DSC) chart of the change. Fig. 3-2 is a view showing a 1H-NMR chart of the inclusion compound obtained in Synthesis Example 3. Fig. 4-1 is a graph showing a thermal analysis (DSC) chart of the temperature change of the inclusion compound obtained in Synthesis Example 4. 4-2 is a view showing a 1H-NMR chart of the inclusion compound obtained in Synthesis Example 4. Fig. 5 is a graph showing a thermal analysis (DSC) chart for synthesizing the temperature change of the inclusion compound obtained in Reference Example 1. Fig. 6 is a view showing a thermal analysis (DSC) chart for synthesizing the temperature change of the inclusion compound obtained in Comparative Example 1. 153278. Doc -39-

Claims (1)

201139358 VII. Patent Application Range: 1. An inclusion compound or a composition thereof comprising the compound (B) comprising the aromatic carboxylic acid compound (A) and the following formula (Π) and (A) and (b) a molar ratio of 1:2 of the inclusion compound, and the inclusion compound accounts for 7 〇 mol% to 1 〇〇 mol% of all the inclusion compounds containing (A) and (B). 1] N (Π) R2 (wherein R2 represents a hydrogen atom, a C1 to C1 alkylene group, an aryl group, an arylalkyl group or a cyanoethyl group, and R_3 to R5 represent a hydrogen atom, a nitro group, a halogen atom, a C1 to C20 alkyl group, A hydroxy-substituted cl~C2 alkyl group, an aryl group, an arylalkyl group or a C1-C20 fluorenyl group; a dotted line represents a single bond or a double bond). 2. The inclusion compound of claim 1 or a composition thereof, wherein the aromatic tickacid compound is a compound represented by the formula (1) or the formula (IV), [Chem. 2] (co〇H) Ni m (wherein nl represents any integer from 1 to 4; n2 represents any integer from 0 to 4; R·6 represents a C1 to C6 alkyl group, a nitro group or a hydroxyl group) [Chem. 3] 153278.doc 201139358 (^7)πι2 (COOH)ml (17) (wherein ml represents an integer of any of 4; m2 represents any integer of 0 to 2; and R7 represents a C1 to C6 alkyl group, a nitro group, a trans group or a formula Base of representation, [Chemical 4] (wherein q represents an integer of 1 or 2' * represents a bonding position)). 3. The inclusion compound of claim 2, or a composition thereof, wherein the above formula (IV) is the following formula (I), [Chem. 5] COOH (wherein R! represents a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a nitro group or a thio group). 4. The inclusion compound of claim 3, or a composition thereof, wherein the above formula (I) is 5-hydroxyisophthalic acid. 5. The inclusion compound or composition thereof according to any one of claims 1 to 4, wherein the above formula (II) is 2-phenyl-4-methyl--5-hydroxymethylimidazole 153278.doc 8 201139358 6. 7. A method of producing an inclusion compound according to claim i or a composition thereof, which comprises adding an aromatic acid compound to the alcohol solution of the compound of the above. A preparation of the inclusion compound of claim 1 or a composition thereof, wherein the compound of (11) is added with a compound of an aromatic acid compound or a cured product thereof, such as a requesting fat. It. Compound or composition thereof, with epoxy tree 153278.doc