JPWO2011089874A1 - Inclusion compound and method for producing the same - Google Patents

Abstract

An object is to provide a high-purity 1: 2 clathrate compound of an aromatic carboxylic acid compound and an imidazole compound, and to provide an epoxy resin composition containing the clathrate compound as a curing agent or a curing accelerator. To do. The aromatic carboxylic acid compound (A) and the imidazole compound (B) are added by adding an aromatic carboxylic acid compound to the alcohol solution of the imidazole compound or by adding an alcohol solution of the aromatic carboxylic acid compound to the imidazole compound. And an inclusion compound containing (A) to (B) in a molar ratio of 1: 2 can be produced with high purity. The clathrate compound thus obtained is useful as a curing agent such as an epoxy resin or a curing accelerator.

Description

The present invention relates to a novel clathrate compound and a method for producing the same, and more particularly to an clathrate compound comprising an aromatic carboxylic acid compound and an imidazole compound useful as an epoxy resin curing catalyst, an epoxy compound containing the clathrate compound and the production method thereof The present invention relates to a resin composition or a cured product thereof.
This application claims priority to Japanese Patent Application No. 2010-10375 filed on January 20, 2010, and Japanese Patent Application No. 2010-228645 filed on October 8, 2010, The contents are incorporated here.

  Epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties. As a curing agent for curing such an epoxy resin, an imidazole compound is used. However, a mixed solution of an epoxy resin and an imidazole compound has a problem that the start of curing is quick and the stability of one liquid is extremely poor. .

  Therefore, as a curing agent, a salt obtained by adding hydroxybenzoic acid to an imidazole compound (see Patent Document 1) or a tetrakisphenol compound (for example, 1,1,2,2-tetrakis (4-hydroxyphenyl)) The use of an inclusion body of ethane (hereinafter referred to as TEP) and an imidazole compound has been proposed (see Patent Document 2). Such imidazole acid addition salts and clathrates have certain effects, but the development of those having the same function or further improved functions has been desired.

  Therefore, the formula (i)

[Wherein, R ₁ represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a nitro group, or a hydroxyl group. An isophthalic acid compound represented by formula (ii)

[Wherein R ₂ represents a hydrogen atom, a C1-C10 alkyl group, an aryl group, an arylalkyl group or a cyanoethyl group, and R _{3 to} R ₅ each independently represent a hydrogen atom, a nitro group, a halogen atom, The C1-C20 alkyl group which may have a substituent, the C1-C20 alkyl group substituted by the hydroxy group, an aryl group, an arylalkyl group, or the C1-C20 acyl group is represented. ] An inclusion compound containing an imidazole compound represented by the formula was proposed and developed (Patent Document 3).

  In the method for producing an inclusion compound in Patent Document 3, after adding an isophthalic acid compound and an imidazole compound to a solvent, the mixture is subjected to a heat treatment or a heat reflux treatment while stirring as necessary, to cause precipitation. In addition, considering the ease of dissolution in a solvent, the document discloses a solution after dissolving an isophthalic acid compound represented by formula (i) and an imidazole compound represented by formula (ii) in a solvent, respectively. It is described that it is preferable to mix them together.

However, in Patent Document 3, the inclusion compound of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole is not specifically described, but is described in the same patent document. When 5-hydroxyisophthalic acid was reacted with 2-phenyl-4-methyl-5-hydroxymethylimidazole by the method, only a mixture of 1: 1 clathrate and 1: 2 clathrate of both compounds was obtained. .
Thereafter, a 1: 1 inclusion compound of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole could be produced with high purity (Patent Document 4), but a 1: 2 inclusion compound was obtained. The compound could not be produced with high purity.

Japanese Patent Publication No.4-2638 JP-A-11-71449 International Publication No. 2008/074427 Pamphlet International Publication No. 2009/037862 Pamphlet

  Therefore, the present invention provides a high-purity 1: 2 clathrate compound of an aromatic carboxylic acid compound such as 5-hydroxyisophthalic acid and an imidazole such as 2-phenyl-4-methyl-5-hydroxymethylimidazole. Is an issue.

  As a result of intensive studies, the present inventors have devised a mixing method of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole so that the molar ratio of host to guest is 1 to 2. It was found that an inclusion compound (hereinafter abbreviated as 1: 2 inclusion compound) was obtained. As a result of further investigation, the inclusion ratio of the host compound and the guest compound of the clathrate compound in which the molar ratio of host to guest is only 1: 1 (hereinafter referred to as 1: 1 clathrate compound) is known. It was found that a 1: 2 clathrate compound can be produced by utilizing the production method of the present invention. Further, as a result of comparing the case where a 1: 2 clathrate compound could not be produced by a known production method and the case where the solubility of an aromatic carboxylic acid compound as a host compound in a solvent was poor, the known method produced 1: 2. It was found that 2 clathrate compounds could not be produced. In addition, the present inventors have found that a curable epoxy resin composition containing the 1: 2 clathrate compound and a cured product thereof can be produced, and the characteristics are improved as compared with the case of containing the 1: 1 clathrate compound. The present invention was completed.

That is, the present invention
(1) Aromatic carboxylic acid compound (A) and formula (II)

(Wherein, _{R 2} is a hydrogen atom, C1 -C10 alkyl group, an aryl group, an arylalkyl group or cyanoethyl _group, R 3 to R ₅ is a hydrogen atom, a nitro group, a halogen atom, C1 to C20 alkyl group Represents a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or an acyl group of C1-C20. The portion with a broken line represents a single bond or a double bond. An inclusion compound containing the compound (B), wherein the molar ratio of (A) to (B) is 1: 2, and the inclusion compound contains (A) and (B) An inclusion compound or a composition thereof which is 70 to 100 mol% in the inclusion compound,
(2) The aromatic carboxylic acid compound is represented by the formula (III)

(Wherein, n1 is .R ₆ is .n2 representing an integer of 1 to 4 representing an integer of 0 to 4 representing the C1~C6 alkyl group, a nitro group or a hydroxyl group.)
Or formula (IV)

(Wherein, m1 is .m2 representing an integer of 1 to 4 represent an integer of 0 to 2 .R ₇ is C1~C6 alkyl group, a nitro group, a hydroxyl group or the following formula

(Wherein q represents an integer of 1 or 2, * represents a bonding position). )
An inclusion compound or a composition thereof according to (1), wherein the inclusion compound is a compound represented by
(3) Formula (IV) is converted to Formula (I)

(Wherein R ₁ represents a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a nitro group or a hydroxy group), or an inclusion compound according to (2) or a composition thereof ,
(4) The inclusion compound or the composition thereof according to the above (3), wherein the formula (I) is 5-hydroxyisophthalic acid, and (5) the formula (II) is 2-phenyl-4- The inclusion compound or composition thereof according to any one of (1) to (4), wherein the inclusion compound is methyl-5-hydroxymethylimidazole.

The present invention also provides:
(6) A method for producing an inclusion compound or a composition thereof according to (1), wherein an aromatic carboxylic acid compound is added to the alcohol solution of the compound of formula (II),
(7) The method for producing an inclusion compound or a composition thereof according to (1) above, wherein an alcohol solution of an aromatic carboxylic acid compound is added to the compound of formula (II),
further,
(8) The present invention relates to a curable epoxy resin composition or a cured product thereof containing the inclusion compound according to any one of (1) to (5) or a composition thereof and an epoxy resin.

It is a figure which shows the thermal analysis (DSC) chart by the temperature change of the clathrate compound obtained by the synthesis example 1. FIG. It is a figure which shows the thermal analysis (DSC) chart by the temperature change of the clathrate compound obtained by the synthesis example 2. FIG. 4 is a diagram showing a ¹ H-NMR chart of an inclusion compound obtained in Synthesis Example 2. FIG. It is a figure which shows the thermal analysis (DSC) chart by the temperature change of the clathrate compound obtained by the synthesis example 3. FIG. 4 is a diagram showing a ¹ H-NMR chart of an inclusion compound obtained in Synthesis Example 3. FIG. It is a figure which shows the thermal analysis (DSC) chart by the temperature change of the clathrate compound obtained by the synthesis example 4. FIG. Is a diagram showing ^{1 H-NMR} chart of the obtained inclusion compound in Example 4. It is a figure which shows the thermal analysis (DSC) chart by the temperature change of the clathrate compound obtained in the synthesis reference example 1. 2 is a diagram showing a thermal analysis (DSC) chart according to temperature change of an inclusion compound obtained in Synthesis Comparative Example 1. FIG.

(Inclusion compound or composition thereof)
The inclusion compound of the present invention or a composition thereof comprises an aromatic carboxylic acid compound (hereinafter abbreviated as “carboxylic acid compound”) as a host compound, and a compound of the formula (II)

(Wherein, _{R 2} is a hydrogen atom, C1 -C10 alkyl group, an aryl group, an arylalkyl group or cyanoethyl _group, R 3 to R ₅ is a hydrogen atom, a nitro group, a halogen atom, C1 to C20 alkyl group Represents a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or an acyl group of C1-C20. The portion with a broken line represents a single bond or a double bond. An inclusion compound in which the molar ratio of the carboxylic acid compound to the imidazole compound is only 1: 2, or the inclusion ratio is 1: 2. It is a composition containing a compound with high purity.

  Inclusion compounds having different molar ratios such as 1: 1 may be mixed into the inclusion compound having a molar ratio of carboxylic acid compound to imidazole compound of 1: 2, and in the present invention, this is the same as the inclusion compound. It is called a composition.

The inclusion compound of the present invention or the composition thereof has a content ratio of 1: 2 inclusion compound of 70 mol% or more, preferably 80 mol% in the entire inclusion compound containing a carboxylic acid compound and an imidazole compound. More preferably, it is 90 mol% or more, more preferably, inclusion compounds of other molar ratio such as 1: 1 are not substantially mixed. However, the clathrate compound of the present invention may contain a third component such as a solvent, and the third component is preferably at most 40 mol%, more preferably at most 10 mol%, Most preferably, it is an inclusion compound containing no components. In the present invention, an inclusion compound refers to a compound in which a host compound forms an inclusion lattice and the host compound is bonded to one or more guest compounds by a bond other than a covalent bond, and more preferably, A crystalline compound. The inclusion compound of the present invention containing a carboxylic acid compound and an imidazole compound can also be referred to as a salt formed from a carboxylic acid compound and an imidazole compound.
As an abbreviation, 5-hydroxyisophthalic acid is referred to as “HIPA”, and 2-phenyl-4-methyl-5-hydroxymethylimidazole is referred to as “2P4MHZ”.

  Here, the inclusion lattice means that the host compounds are bonded to each other by bonds other than covalent bonds, and other molecules (guests, solvents, etc.) A host compound in which a molecule and a host compound are included by a bond other than a covalent bond, or a host compound and another molecule (guest, solvent, etc.) are bound by a bond other than a covalent bond and bound to another molecule. A compound in which a host compound and / or another molecule (guest, solvent, etc.) is included by a bond other than a covalent bond in a gap between two molecules or three or more molecules.

  The clathrate compound of the present invention can be used as a resin curing agent such as a polyester resin, an epoxy resin, and an epoxy / polyester resin, and can be particularly suitably used as a curing agent for an epoxy resin. The epoxy resin composition of the present invention is used for curing epoxy resins, such as epoxy resin adhesives, semiconductor encapsulants, liquid crystal encapsulants, printed wiring laminates, varnishes, casting materials, inks, etc. It can be preferably used. The clathrate compound of the present invention may be in the form of a liquid dissolved in a solvent, but is preferably in the form of a powder (deposited in the solvent). By being in a powder form, it can be used for, for example, a powder coating.

The structure of the inclusion compound can be confirmed by thermal analysis (TG and DTA), infrared absorption spectrum (IR), X-ray diffraction (XRD) pattern, solid NMR spectrum, and the like. The composition of the clathrate compound can be confirmed by thermal analysis, ¹ H-NMR spectrum, high performance liquid chromatography (HPLC), elemental analysis or the like.

Further, the content ratio (purity) of the 1: 2 clathrate compound is, for example, in the case of a composition comprising a 1: 1 clathrate compound and a 1: 2 clathrate compound, the integration of ¹ H-NMR of the clathrate compound. From the value, it can be calculated as purity (%) = 1: 2 inclusion compound / (1: 1 inclusion compound + 1: 2 inclusion compound) × 100. As an example, the first and HIPA and 2P4MHZ: purity 2 clathrates, among _{DMSO-d 6,} using a value obtained by dividing (a) the integral value of 7.5ppm an integral value of 2.1ppm at 25 ° C. The following equation can be used.
1: 2 purity of clathrate compound (%) = (2a / 3-1) × 100

(Carboxylic acid compound)
It does not restrict | limit especially as an aromatic carboxylic acid compound, For example, the following can be illustrated.
Benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2-n-propylbenzoic acid, 3-n -Propylbenzoic acid, 4-n-propylbenzoic acid, 2-butylbenzoic acid, 3-butylbenzoic acid, 4-butylbenzoic acid, 2-i-propylbenzoic acid, 3-i-propylbenzoic acid, 4-i -Propylbenzoic acid, 2-i-butylbenzoic acid, 3-i-butylbenzoic acid, 4-i-butylbenzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-nitro Benzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, methyl 2-nitrobenzoate, methyl 3-nitrobenzoate, methyl 4-nitrobenzoate, ethyl 2-nitrobenzoate, 3-nitrobenzoic acid Ethyl benzoate, ethyl 4-nitrobenzoate, propyl 2-nitrobenzoate, propyl 3-nitrobenzoate, propyl 4-nitrobenzoate, butyl 2-nitrobenzoate, butyl 3-nitrobenzoate, 4-nitrobenzoate Acid butyl, 2,3-dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 2,5-dimethylbenzoic acid, 2,6-dimethylbenzoic acid, 3,4-dimethylbenzoic acid, 3,5-dimethylbenzoic acid 3,6-dimethylbenzoic acid, 4,5-dimethylbenzoic acid, 4,6-dimethylbenzoic acid, 2,3-diethylbenzoic 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-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 3, , 6-dihydroxybenzoic acid, 4,5-dihydroxybenzoic acid, 4,6-dihydroxybenzoic acid;

  Phthalic acid, 3-methylphthalic acid, 4-methylphthalic acid, 5-methylphthalic acid, 6-methylphthalic acid, 3-ethylphthalic acid, 4-ethylphthalic acid, 5-ethylphthalic acid, 6-ethylphthalic acid, 3-n-propylphthalic acid 4-n-propylphthalic acid, 5-n-propylphthalic acid, 6-n-propylphthalic acid, 3-butylphthalic acid, 4-butylphthalic acid, 5-butylphthalic acid, 6-butylphthalic acid, 3-i-propyl Phthalic acid, 4-i-propylphthalic acid, 5-i-propylphthalic acid, 6-i-propylphthalic acid, 3-i-butylphthalic acid, 4-i-butylphthalic acid, 5-i-butylphthalic acid, 6- i-butylphthalic acid, 3-hydroxyphthalic acid, 4-hydroxyphthalic acid, 5-hydroxyphthalic acid, 6-hydroxyphthalic acid, 3,4-dihydro Siphthalic acid, 3,5-dihydroxyphthalic acid, 3,6-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 4,6-dihydroxyphthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, 5-nitrophthalic acid, 6-nitrophthalic acid, 3,4-dimethylphthalic acid, 3,5-dimethylphthalic acid, 3,6-dimethylphthalic acid, 4,5-dimethylphthalic acid, 4,6-dimethylphthalic acid;

  Isophthalic acid, 2-methylisophthalic acid, 4-methylisophthalic acid, 5-methylisophthalic acid, 6-methylisophthalic acid, 2-ethylisophthalic acid, 4-ethylisophthalic acid, 5-ethylisophthalic acid, 6-ethylisophthalic acid 2-n-propylisophthalic acid, 4-n-propylisophthalic acid, 5-n-propylisophthalic acid, 6-n-propylisophthalic acid, 2-i-propylisophthalic acid, 4-i-propylisophthalic acid, 5 -I-propylisophthalic acid, 6-i-propylisophthalic acid, 2-butylisophthalic acid, 4-butylisophthalic acid, 5-butylisophthalic acid, 6-butylisophthalic acid, 2-i-butylisophthalic acid, 4-i -Butylisophthalic acid, 5-i-butylisophthalic acid, 6-i-butylisophthalic acid, 4-t-buty Isophthalic acid, 5-t-butylisophthalic acid, 6-t-butylisophthalic acid, 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 6-hydroxyisophthalic acid, 2,4-dihydroxyisophthalic acid 2,5-dihydroxyisophthalic acid, 2,6-dihydroxyisophthalic acid, 4,5-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 5,6-dihydroxyisophthalic acid, 2,4-dimethylisophthalic acid, 2 , 5-dimethylisophthalic acid, 2,6-dimethylisophthalic acid, 4,5-dimethylisophthalic acid, 4,6-dimethylisophthalic acid, 5,6-dimethylisophthalic acid, 2-nitroisophthalic acid, 4-nitroisophthalic acid 5-nitroisophthalic acid, 6-nitroisophthalic acid, 2 Methyl terephthalic acid, 2-ethyl terephthalic acid, 2-n-propyl terephthalic acid, 2-i-propyl terephthalic acid, 2-butyl terephthalic acid, 2-i-butyl terephthalic acid, 2-hydroxyterephthalic acid, 2,6- Dihydroxyterephthalic acid, 2,6-dimethylterephthalic acid, 2-nitroterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid (trimetic acid), 1,2,5-benzenetricarboxylic acid Acid, 1,3,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid (trimesic acid), 4-hydroxy-1,2,3-benzenetricarboxylic acid, 5-hydroxy-1,2,3- Benzenetricarboxylic acid, 3-hydroxy-1,2,4-benzenetricarboxylic acid, 5-hydroxy-1,2,4 -Benzenetricarboxylic acid, 6-hydroxy-1,2,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid);

1-naphthoic acid, 2-naphthoic acid, 2-methyl-1-naphthoic acid, 3-methyl-1-naphthoic acid, 4-methyl-1-naphthoic acid, 5-methyl-1-naphthoic acid, 6-methyl- 1-naphthoic acid, 7-methyl-1-naphthoic acid, 8-methyl-1-naphthoic acid, 1-methyl-2-naphthoic acid, 3-methyl-2-naphthoic acid, 4-methyl-2-naphthoic acid, 5-methyl-2-naphthoic acid, 6-methyl-2-naphthoic acid, 7-methyl-2-naphthoic acid, 8-methyl-2-naphthoic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid Acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Carboxylic acid, 2,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid, 2-hydroxy-1-naphtho Acid, 3-hydroxy-1-naphthoic acid, 4-hydroxy-1-naphthoic acid, 5-hydroxy-1-naphthoic acid, 6-hydroxy-1-naphthoic acid, 7-hydroxy-1-naphthoic acid, 8-hydroxy -1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid 7-hydroxy-2-naphthoic acid, 8-hydroxy-2-naphthoic acid, 1,2,4,5-naphthalene terecarboxylic acid, 2 3-dihydroxy-1-naphthoic acid, 2,4-dihydroxy-1-naphthoic acid, 2,5-dihydroxy-1-naphthoic acid, 2,6-dihydroxy-1-naphthoic acid, 2,7-dihydroxy-1- Naphthoic acid, 2,8-dihydroxy-1-naphthoic acid, 3,4-dihydroxy-1-naphthoic acid, 3,5-dihydroxy-1-naphthoic acid, 3,6-dihydroxy-1-naphthoic acid, 3,7 -Dihydroxy-1-naphthoic acid, 3,8-dihydroxy-1-naphthoic acid, 4,5-dihydroxy-1-naphthoic acid, 4,6-dihydroxy-1-naphthoic acid, 4,7-dihydroxy-1-naphthoic acid Acid, 4,8-dihydroxy-1-naphthoic acid, 5,6-dihydroxy-1-naphthoic acid, 5,7-dihydroxy-1-naphthoic acid, 5,8-dihydroxy-1 Naphthoic acid, 6,7-dihydroxy-1-naphthoic acid, 6,8-dihydroxy-1-naphthoic acid, 7,8-dihydroxy-1-naphthoic acid, 1,3-dihydroxy-2-naphthoic acid, 1, 4-dihydroxy-2-naphthoic acid, 1,5-dihydroxy-2-naphthoic 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-dihydroxy-2-naphthoic acid, 3,6-dihydroxy-2-naphthoic acid, 3,8-dihydroxy-2-naphthoic acid, 4,5 -Dihydroxy-2-naphthoic acid, 4,6-dihydroxy-2-naphthoic acid, 4,7-dihydroxy-2-naphthoic acid, 4,8-dihydroxy-2-naphthoic acid, 5,6 Dihydroxy-2-naphthoic acid, 5,7-dihydroxy-2-naphthoic acid, 5,8-dihydroxy-2-naphthoic acid, 6,7-dihydroxy-2-naphthoic acid, 6,8-dihydroxy-2-naphthoic acid 7,8-dihydroxy-2-naphthoic acid, cyclohexanecarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1, 2-decahydronaphthalenedicarboxylic acid, 1,3-decahydronaphthalenedicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 1,6-decahydronaphthalenedicarboxylic acid, 1, 7-decahydronaphthalenedicarboxylic acid, 1,8-decahydronaphth Such as dicarboxylic acid.
These aromatic carboxylic acid compounds may be used alone or in combination of two or more.

  Of these, the formula (III)

(Wherein, n1 is .R ₆ is .n2 representing an integer of 1 to 4 representing an integer of 0 to 4 representing the C1~C6 alkyl group, a nitro group or a hydroxyl group.)
Or formula (IV)

(Wherein, m1 is .m2 representing an integer of 1 to 4 represent an integer of 0 to 2 .R ₇ is C1~C6 alkyl group, a nitro group, a hydroxyl group or the following formula

(Wherein q represents an integer of 1 or 2, * represents a bonding position). It is preferable that it is an aromatic carboxylic acid compound represented by this.
The C1-C6 alkyl group of R ₆ and R ₇ includes a cycloalkyl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i- Butyl group, s-butyl group, t-butyl group, cyclobutyl group, cyclopropylmethyl group, n-pentyl group, i-pentyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, n-hexyl group, Examples include i-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group and the like.

  Further, in formula (III), formula (I)

It is preferable that it is an aromatic carboxylic acid compound represented by these.
In the formula, _{R 1} represents a C1 -C6 alkyl group, C1 -C6 alkoxy group or a hydroxy group.

  The C1-C6 alkyl group is preferably a C1-C4 alkyl group and may have a substituent. C1-C6 alkyl groups include cycloalkyl groups, specifically methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl. Group, t-butyl group, cyclobutyl group, cyclopropylmethyl group, n-pentyl group, i-pentyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, n-hexyl group, i-hexyl group, 4 -Methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2 -A dimethylbutyl group, a 1, 3- dimethylbutyl group, a 2, 3- dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group etc. can be mentioned.

  The C1-C6 alkoxy group is preferably a C1-C4 alkoxy group, and may have a substituent. Specific examples of the C1-C6 alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n- Pentoxy group, i-pentoxy group, 2-methylbutoxy group, 1-ethylpropoxy group, 2-ethylpropoxy group, neopentoxy group, n-hexyloxy group, 4-methylpentoxy group, 3-methylpentoxy group, 2 -Methylpentoxy group, 3,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3- Examples thereof include a dimethylbutoxy group.

(Imidazole compound)
The imidazole compound used in the present invention has the formula (II)

It is an imidazole compound and an imidazoline compound represented by these.
Specifically, the formula (II) is

Containing the structure.
In the formula, R ₂ represents a hydrogen atom, a C1-C10 alkyl group, an aryl group, an arylalkyl group or a cyanoethyl group, and is preferably a hydrogen atom.

  The C1-C10 alkyl group is preferably a C1-C6 alkyl group, and may have a substituent. Specific examples of the C1-C10 alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n- A pentyl group, n-hexyl group, nonyl group, i-nonyl group, decyl group and the like can be mentioned.

  An aryl group means a monocyclic or polycyclic aryl group. Here, in the case of a polycyclic aryl group, a partially saturated group is included in addition to the fully unsaturated group. Examples thereof include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group. Of these, a C6-C10 aryl group is preferable. The aryl group may have a substituent.

  The arylalkyl group is a group in which the aryl group and the alkyl group are bonded, and includes a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 1-phenyl-n-hexyl group, a naphthalen-1-ylmethyl group, Examples include naphthalen-2-ylethyl group, 1-naphthalen-2-yl-n-propyl group, and inden-1-ylmethyl group. Of these, a C6-C10 aryl C1-C6 alkyl group is preferable. The arylalkyl group may have a substituent.

R _{3 to} R ₅ are each independently a hydrogen atom, a nitro group, a halogen atom, a C1 to C20 alkyl group, a C1 to C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C1 to C20 group. Represents an acyl group.

  Examples of the C1-C20 alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n -Hexyl group, nonyl group, i-nonyl group, decyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like can be mentioned. Preferably, it is a C1-C10 alkyl group.

Examples of the aryl group and arylalkyl group include the same groups as those in R ₂ .

  The C1-C20 acyl group means a group in which a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or the like is bonded to a carbonyl group. Acyl group is, for example, formyl group; acetyl group, propionyl group, butyroyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, 3-methylnonanoyl group, 8-methylnonanoyl group, 3-ethyl Octanoyl group, 3,7-dimethyloctanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, 1-methylpentadecanoyl group, 14-methylpentadecane Alkylcarbonyl such as noyl group, 13,13-dimethyltetradecanoyl group, heptadecanoyl group, 15-methylhexadecanoyl group, octadecanoyl group, 1-methylheptadecanoyl group, nonadecanoyl group, icosanoyl group and heinacosanoyl group Alkenylcarbonyl groups such as acryloyl group, methacryloyl group, allylcarbonyl group and cinnamoyl group; alkynylcarbonyl groups such as ethynylcarbonyl group and propynylcarbonyl group; arylcarbonyls such as benzoyl group, naphthylcarbonyl group, biphenylcarbonyl group and anthranylcarbonyl group Group; heteroarylcarbonyl groups such as 2-pyridylcarbonyl group and thienylcarbonyl group; and the like. Among these, a C1-C20 (including carbonyl group) acyl group is preferable, and a C1-C6 acyl group is particularly preferable.

  Specifically, as the imidazole compound represented by the formula (II), imidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2- Undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole Etc. 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole 2-phenylimidazole or 2-phenyl-4,5-dihydroxymethylimidazole is preferred.

  Examples of the imidazoline compound represented by the formula (II) include 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-ethylimidazoline, 2-i-propylimidazoline, 2,4- Examples thereof include dimethylimidazoline and 2-phenyl-4-methylimidazoline, and 2-methylimidazoline or 2-phenylimidazoline is preferable.

(Method for producing 1: 2 inclusion compound of carboxylic acid compound vs. imidazole compound or composition thereof)
A 1: 2 inclusion compound or a composition thereof substantially comprising a carboxylic acid compound versus an imidazole compound can be obtained by the following method or the like.
(1) Method of adding an alcohol solution of a carboxylic acid compound to an imidazole compound (2) Method of adding a carboxylic acid compound to an alcohol solution of an imidazole compound

Details of the method (1) will be described below.
An alcohol solution of a carboxylic acid compound is added to the imidazole compound while stirring as necessary. The addition of the alcohol solution of the carboxylic acid compound is not particularly limited, but it is usually added continuously or dividedly over 5 to 120 minutes.
After the addition of the alcohol solution of the carboxylic acid compound, the solution is allowed to stand at room temperature for 0 to 5 hours as necessary, and heated at room temperature to 40 ° C. for 0 to 5 hours or refluxed for 0 to 5 hours.
As a compounding ratio of the carboxylic acid compound and the imidazole compound, the imidazole compound (guest) is preferably 0.1 to 5.0 mol with respect to 1 mol of the carboxylic acid compound (host), and 0.5 to 3 More preferably, it is 0.0 mol.

Examples of the alcohol solvent include lower alcohols such as methanol, ethanol and n-propanol, but methanol is preferred. The amount used is usually 0.5 to 50 times the weight of the carboxylic acid compound.
In the step after the heat treatment or the heat reflux treatment, for example, the solid compound may be precipitated by simply stopping the heat treatment or the heat reflux treatment, but after heating, it is preferably left overnight at room temperature. After precipitating the solid compound, the target compound is obtained by, for example, filtering and drying.

Details of the method (2) will be described below.
After the imidazole compound is suspended or dissolved in alcohol (the alcohol suspension and the alcohol solution are referred to as an alcohol solution), the carboxylic acid compound is added with stirring as necessary. The addition of the carboxylic acid compound is not particularly limited, but it is usually added continuously or dividedly over 5 to 120 minutes.
After the addition of the carboxylic acid compound, the mixture is allowed to stand at room temperature for 0 to 5 hours as necessary, and heated at room temperature to 40 ° C. for 0 to 5 hours or refluxed for 0 to 5 hours.

  As a compounding ratio of the carboxylic acid compound and the imidazole compound, the imidazole compound (guest) is preferably 0.1 to 5.0 mol with respect to 1 mol of the carboxylic acid compound (host), and 0.5 to 3 More preferably, it is 0.0 mol.

  Examples of the alcohol solvent include lower alcohols such as methanol, ethanol and n-propanol, but methanol is preferred. The amount used is usually 0.5 to 50 times the weight of the carboxylic acid compound.

For reference, a method for producing an inclusion compound having a molar ratio of HIPA to 2P4MHZ of 1: 1 is described below.
(Method for producing an inclusion compound having a molar ratio of HIPA to 2P4MHZ of 1: 1)
An inclusion compound substantially having a molar ratio of HIPA to 2P4MHZ of only 1: 1 can be obtained by the following method or the like.
After HIPA is dissolved in alcohol, 2P4MHZ is added with stirring as necessary. The addition of 2P4MHZ is not particularly limited, but it is usually added for 5 minutes or longer, preferably 5 minutes to 120 minutes continuously or dividedly.
After the addition of 2P4MHZ, the mixture is allowed to stand at room temperature for 0 to 5 hours as necessary, and heated at room temperature to 40 ° C. for 0 to 5 hours or refluxed for 0 to 5 hours.

  As a blending ratio of HIPA and 2P4MHZ in the method for producing a 1: 1 clathrate compound, 2P4MHZ (guest) is preferably 0.1 to 5.0 mol with respect to 1 mol of HIPA (host). More preferably, it is 5-3.0 mol.

  Examples of the alcohol solvent in the production method of the 1: 1 clathrate compound include lower alcohols such as methanol, ethanol and n-propanol, but methanol is preferred. The amount used is usually 0.5 to 50 times the amount of HIPA.

  In the step after the heat treatment or the heat reflux treatment, for example, the solid compound may be precipitated by simply stopping the heat treatment or the heat reflux treatment, but after heating, it is preferably left overnight at room temperature. After precipitating the solid compound, the target compound is obtained by, for example, filtering and drying.

(Curable epoxy resin composition)
The clathrate compound of the present invention or a composition thereof can be mixed with an epoxy resin as an epoxy resin curing agent or curing accelerator and used as, for example, a semiconductor sealing agent.
The cured epoxy resin composition used as a semiconductor encapsulant or the like contains an epoxy resin, an inclusion compound of the present invention, and, if necessary, other additives.

1) Epoxy resin As the epoxy resin, various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propanediglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propanediglycidyl Ether, bis (4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, bis Resorcinol tetraglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropro Pandiglycidyl ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2, 3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4′-bis (2,3-epoxypropoxy) octafluorobiphenyl, phenol novolac type bisepoxy compounds, etc. Aromatic glycidyl ether compounds, alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxy carboxylates, vinylcyclohexene dioxide, and other alicyclic polyepoxy compounds, diglycidyl phthalate, diglycidyl tetrahydrophthalate Diglycidyl hexahydride Glycidyl ester compounds such as lophthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3-dicarboxylate, dimer acid glycidyl ester, diglycidyl aniline, diglycidyl toluidine, Examples thereof include glycidylamine compounds such as triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, diglycidyltribromoaniline, and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate.

  Examples of liquid epoxy resins include polyalkylene ether type epoxy compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, dimer acid diglycidyl ester, and phthalic acid diester. Examples include glycidyl ester-type epoxy compounds such as glycidyl ester and tetrahydrophthalic acid diglycidyl ester, copolymers such as glycidyl (meth) acrylate and allyl glycidyl ether, and copolymers of the monomer and other soft unsaturated monomers. Can do. Soft unsaturated monomers are those whose homopolymer has a glass transition temperature of less than 60 ° C., for example, methyl acrylate, ethyl acrylate, butyl (meth) acrylate, i-butyl (meth) acrylate, ( Examples thereof include 2-ethylhexyl (meth) acrylate and lauryl methacrylate.

2) Inorganic filler The epoxy resin composition of this invention should just contain the said clathrate compound and an epoxy resin, and is an epoxy resin composition containing an inorganic filler in addition to the clathrate compound and an epoxy resin. There may be.

  Although it does not restrict | limit especially as an inorganic filler, For example, quartz glass, the spherical silica obtained by melting by flame, the spherical silica manufactured by a sol gel method, crystalline silica, alumina, talc, ammonium nitride, silicon nitride, magnesia, A magnesium silicate etc. are mentioned, These may be used independently or may use 2 or more types.

3) Curing agent or effect accelerator The epoxy resin composition of the present invention may further contain a curing accelerator or a curing agent in addition to the inclusion compound.

  The curing agent that may be contained in the epoxy resin composition of the present invention is not particularly limited as long as it is a compound that reacts with an epoxy group in the epoxy resin to cure the epoxy resin. Similarly, the curing accelerator that may be contained in the epoxy resin composition of the present invention is not particularly limited as long as it is a compound that accelerates the curing reaction. As such a curing agent or curing accelerator, an arbitrary one can be selected from those conventionally used as curing agents or curing accelerators for conventional epoxy resins. For example, amine compounds such as aliphatic amines, alicyclic and heterocyclic amines, aromatic amines, modified amines, imidazole compounds, imidazoline compounds, amide compounds, ester compounds, phenol compounds , Alcohol compounds, thiol compounds, ether compounds, thioether compounds, urea compounds, thiourea compounds, Lewis acid compounds, phosphorus compounds, acid anhydride compounds, onium salt compounds, active silicon compounds An aluminum complex etc. are mentioned.

Specific examples of the curing agent or curing accelerator include the following compounds.
Examples of aliphatic amines include ethylenediamine, trimethylenediamine, triethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, Trimethylhexamethylenediamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine , N, N-dimethylcyclohexylamine, dibutylaminopropylamine, dimethylaminoethoxyethoxy, triethanolamine, dimethylaminohexanol, and the like.

  Examples of alicyclic and heterocyclic amines include piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis (4-aminocyclohexyl) methane , N, N′-dimethylpiperazine, 1,8-diazabicyclo [4.5.0] undecene-7, and the like.

  Examples of aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline, α- And methylbenzylmethylamine.

  Examples of the modified amines include epoxy compound-added polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-capped polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine. Complex, boron trifluoride-monoethylamine complex, etc. are mentioned.

  Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-i-propylimidazole, 2-i-propylimidazole, 1-n-butylimidazole, 2-n-butyl Imidazole, 1-i-butylimidazole, 2-i-butylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4- Methylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-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-hydroxymethylimidazole 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, etc. Can be mentioned.

  Examples of the imidazoline-based compound include 2-methylimidazoline, 2-phenylimidazoline, and the like.

  Examples of the amide compound include polyamide obtained by condensation of dimer acid and polyamine.

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

  Examples of phenol compounds, alcohol compounds, thiol compounds, ether compounds, and thioether compounds include phenol resin curing agents, aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins, and phenol novolac resins. , Novolac type phenol resins such as cresol novolac resin, these modified resins, for example, epoxidized or butylated novolac type phenol resin, dicyclopentadiene modified phenol resin, paraxylene modified phenol resin, triphenol alkane type phenol resin, Examples thereof include functional phenol resins. In addition, polyol, polymercaptan, polysulfide, 2- (dimethylaminomethylphenol), 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol tri-2- And ethyl hexyl hydrochloride.

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

  Examples of phosphorus compounds include organic phosphine compounds, for example, alkylphosphine such as ethylphosphine and butylphosphine, first phosphine such as phenylphosphine, dialkylphosphine such as dimethylphosphine and dipropylphosphine, diphenylphosphine such as diphenylphosphine, and methylethylphosphine. 2 phosphine; tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, and the like.

  Examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride. Acid, maleic anhydride, tetramethylene maleic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic anhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (Anhydro trimellitate), methylcyclohexene tetracarboxylic acid anhydride, polyazeline acid anhydride and the like.

  Examples of onium salt compounds and active silicon compounds-aluminum complexes include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triphenylsilanol-aluminum complexes, triphenylmethoxysilane-aluminum complexes, and silyl peroxides. An aluminum complex, a triphenylsilanol-tris (salicylide aldehyde) aluminum complex, etc. are mentioned.

  As the curing agent or curing accelerator, it is particularly preferable to use an amine compound, an imidazole compound, or a phenol compound. Among phenolic compounds, it is more preferable to use a phenol resin curing agent.

4) Other additives In addition to those described above, the epoxy resin composition of the present invention includes a plasticizer, an organic solvent, a reactive diluent, an extender, a filler, a reinforcing agent, a pigment, and a flame retardant as necessary. Various additives such as a thickener and a release agent can be blended. Other additives include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxy. Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane Silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane; Um, light calcium carbonate, natural silica, synthetic silica, fused silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc, mica, wollastonite, potassium titanate, aluminum borate , Sepiolite, Zonotolite, etc .; NBR, polybutadiene, chloroprene rubber, silicone, crosslinked NBR, crosslinked BR, acrylic, core shell acrylic, urethane rubber, polyester elastomer, functional group-containing liquid NBR, liquid polybutadiene, liquid polyester, liquid polysulfide , Elastomer modifiers such as modified silicones and urethane prepolymers;

  Hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyl oxide, bis (pentabromo) phenylethane, tris (tribromophenoxy) Triazine, ethylenebistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, polypentabromobenzyl acrylate, triphenyl phosphate, tricresyl phosphate, trixinyl phosphate, cresyl diphenyl Phosphate, xylyldiphenyl phosphate, cresyl bis (di-2,6-xylenyl) phosphate Fate, 2-ethylhexyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, resorcinol bis (di-2,6-xylenyl) phosphate, tris (chloroethyl) phosphate, Tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromopropyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, anionic oxalic acid treated aluminum hydroxide, nitrate treated Aluminum hydroxide, high-temperature hydrothermal treatment aluminum hydroxide, stannic acid surface treatment hydrated metal compound, nickel compound surface treatment magnesium hydroxide, silicone poly -Flame retardants such as surface treated magnesium hydroxide, procovite, multilayer surface treated hydrated metal compound, cationic polymer treated magnesium hydroxide; high density polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, nylon 6, 6. Engineering plastics such as polyacetal, polyethersulfone, polyetherimide, polybutylene terephthalate, polyetheretherketone, polycarbonate, polysulfone; plasticizer; n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl Diluents such as ether, dicyclopentadiene diepoxide, phenol, cresol, t-butylphenol; extenders; reinforcing agents; colorants; thickeners; higher fatty acids, Higher fatty acid esters, higher fatty acid calcium, and the like, for example, mold release agents such as carnauba wax and polyethylene wax; The blending amount of these additives is not particularly limited, and the blending amount can be appropriately determined within the limit that the effects of the present invention can be obtained.

  Furthermore, the epoxy resin composition of the present invention may contain other resins in addition to the epoxy resin. Examples of other resins include polyester resins, acrylic resins, silicone resins, polyurethane resins, and the like.

5) Preparation of epoxy resin composition and cured product thereof The compounding ratio of the epoxy resin and the clathrate compound of the present invention or the composition thereof is in the clathrate compound or the composition thereof with respect to 1 mol of the epoxy ring of the epoxy resin. The imidazole compound is preferably contained in an amount of 0.01 to 1.0 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.3 to 1.0 mol.

  Moreover, although the composition for epoxy cured resin formation can be manufactured by mixing an epoxy resin and the clathrate compound of this invention, or its composition, it is usually 60 ~ so that sufficient mixing state may be formed. Heat to about 100 ° C. and mix. In the production of an epoxy cured resin, the stability of one liquid at this temperature is important. The produced epoxy resin composition may be solid or liquid depending on its composition and production method.

  The curing method of the epoxy cured resin forming composition is not particularly limited as long as it is a method of curing the epoxy cured resin forming composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 ~ 250 ° C.

Examples will be described below, but the technical scope of the present invention is not limited to these examples.
In the following Examples, ¹ HNMR was measured at 25 ° C. using DMSO-d ₆ or MeOH-d ₄ as a measurement solvent.

1 Production of inclusion compound [Synthesis Example 1]
2P4MHZ 20.67 g (109.8 mmol) was added to the flask, and then half of the solution obtained by dissolving HIPA 20 g (109.8 mmol) in 170 ml of methanol was added with stirring. The mixture was washed with 11 mL of methanol and allowed to stand at room temperature for 0.5 hour, and then the remaining HIPA methanol solution was added with stirring, washed with 11 mL of methanol, allowed to stand at room temperature for 0.5 hour, and heated to reflux for 3 hours. Then, after standing overnight at room temperature, 28.89 g of the product was obtained by filtration and vacuum drying (yield 71%). When the obtained product was analyzed by ¹ HNMR, X-ray diffraction and thermal analysis (DSC), it was a clathrate crystal of HIPA: 2P4MHZ of 1: 2. The purity of the 1: 2 clathrate compound was 91%. The thermal analysis (DSC) chart by the temperature change of the obtained clathrate compound is shown in FIG.

[Synthesis Example 2]
Into the flask, 20 g of HIPA (54.9 mmol) was added over 20 minutes with stirring to an alcohol solution obtained by adding 20.67 g (109.8 mmol) of 2P4MHZ and 130 ml of methanol to the flask. After standing at room temperature for 0.5 hour, the mixture was heated to reflux for 3 hours. Then, after standing overnight at room temperature, 29.91 g of the product was obtained by filtration and vacuum drying (yield 97.5%). When the obtained product was analyzed by ¹ HNMR, X-ray diffraction and thermal analysis (DSC), it was a clathrate crystal of HIPA: 2P4MHZ of 1: 2. The purity of the 1: 2 clathrate compound was 97%. A thermal analysis (DSC) chart and a ¹ HNMR chart by temperature change of the obtained clathrate compound are shown in FIGS. 2-1 and 2-2.

[Synthesis Example 3]
2P4MHZ 20.67 g (109.8 mmol) was added to the flask, and then a solution obtained by dissolving 10 g (54.9 mmol) of HIPA in 130 ml of methanol was added over 15 minutes while stirring. After standing at room temperature for 0.5 hour, the mixture was heated to reflux for 3 hours. Then, after standing overnight at room temperature, 29.74 g of the product was obtained by filtration and vacuum drying (yield 97%). When the obtained product was analyzed by ¹ HNMR, X-ray diffraction and thermal analysis (DSC), it was a clathrate crystal of HIPA: 2P4MHZ of 1: 2. The purity of the 1: 2 clathrate compound was 99%. The thermal analysis (DSC) chart and the ¹ HNMR chart by the temperature change of the obtained clathrate compound are shown in FIGS. 3-1 and 3-2.

[Synthesis Example 4]
An inclusion compound with HIPA: Im of 1: 2 was obtained in the same manner as in Synthesis Example 2 except that 7.48 g (109.8 mmol) of unsubstituted imidazole (hereinafter referred to as Im) was used instead of 2P4MHZ. . The purity of the 1: 2 clathrate compound was 77%. The thermal analysis (DSC) chart and ¹ HNMR chart by temperature change of the obtained clathrate compound are shown in FIGS. 4-1 and 4-2.

[Synthesis Reference Example 1] (Preparation of 1: 1 inclusion compound)
20P (109.8 mmol) of HIPA and 126 ml of methanol were added to the flask and mixed, and 20.67 g (109.8 mmol) of 2P4MHZ was added over 15 minutes while stirring. After standing at room temperature for 2 hours, the mixture was heated to reflux for 3 hours. Then, after standing overnight at room temperature, 39.56 g of the product was obtained by filtration and vacuum drying (yield 97.3%). The obtained product was analyzed by ¹ HNMR, X-ray diffraction, and thermal analysis (DSC). As a result, HIPA: 2P4MHZ was a 1: 1 clathrate crystal. The purity of the 1: 2 clathrate compound was 0%. The thermal analysis (DSC) chart by the temperature change of the obtained clathrate compound is shown in FIG.

[Synthesis Reference Example 2]
An inclusion compound with HIPA: Im of 1: 1 was obtained in the same manner as in Synthesis Reference Example 1 except that lm7.48 g (109.8 mmol) was used instead of 2P4MHZ.

[Synthesis Comparative Example 1] (Preparation of mixture of 1: 1 and 1: 2 inclusion compound)
The flask was charged with 36.43 g (200 mmol) of HIPA, 37.65 g (200 mmol) of 2P4MHZ and 230 ml of methanol, stirred and heated to reflux for 3 hours. Then, after standing overnight at room temperature, 64.41 g of the product was obtained by filtration and vacuum drying (yield 87.2%). The obtained product was analyzed by ¹ HNMR, X-ray diffraction and thermal analysis (DSC). As a result, it showed different data from those in Examples 1 and 2. Therefore, HIPA: 2P4MHZ was 1: 1 with the inclusion compound. The crystal was judged to be a mixture of two clathrate compounds. The purity of the 1: 2 clathrate compound was 18%. The thermal analysis (DSC) chart by the temperature change of the obtained clathrate compound is shown in FIG.

2 Production of Epoxy Resin Composition 2-1 Production of Biphenyl Type Epoxy Resin Composition [Composition Reference Example 1]
The inclusion compound obtained by the method of Synthesis Reference Example 1 was 0.249 g in terms of imidazole, 12.445 g of YX4000H (manufactured by Mitsubishi Chemical Corporation) as a biphenyl type epoxy resin, and TOWAX (registered trademark) 131 (Toa) as a release agent. 0.249 g made by Kasei Co., Ltd., 179.97 g FB-940 spherical silica (made by Denki Kagaku Kogyo Co., Ltd.) as filler, 0.383 g LS2940 (manufactured by Shin-Etsu Chemical Co., Ltd.), Novolac as a curing agent Phenol PSM-4261 OH equivalent 103 (manufactured by Gunei Chemical Industry Co., Ltd.) 6.701 g was heated and kneaded at 100 ° C. for 5 minutes, cooled and pulverized to produce a biphenyl type epoxy resin composition.

[Composition Example 1]
The biphenyl type epoxy resin composition is the same as the composition reference example 1 except that the clathrate compound obtained by the method of Synthesis Example 1 is used instead of the clathrate compound obtained by the method of Synthesis Reference Example 1. Manufactured.

2-2 Production of o-cresol novolac type epoxy resin composition [Composition Reference Example 2]
0.378 g of the clathrate compound obtained by the method of Synthesis Reference Example 1 in terms of imidazole, EOCN-1020-55 epoxy equivalent 191-201 (manufactured by Nippon Kayaku Co., Ltd.) 18.886 g as o-cresol novolac epoxy resin, 0.378 g of TOWAX (registered trademark) 131 (manufactured by Toa Kasei Co., Ltd.) as a release agent, 169.97 g of FB-940 spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd.) as a filler, and LS-2940 (Shin-Etsu) as a silane coupling agent 0.944 g (manufactured by Kagaku Co., Ltd.) and 9.443 g of novolak phenol PSM-4261 OH equivalent 103 (manufactured by Gunei Chemical Industry Co., Ltd.) as a curing agent were heated and kneaded at 100 ° C. for 5 minutes, cooled, pulverized and biphenyl type An epoxy resin composition was produced.

[Composition Example 2]
An o-cresol novolac-type epoxy similar to the composition reference example 2 except that the clathrate compound obtained by the method of synthesis example 1 is used instead of the clathrate compound obtained by the method of synthesis reference example 1. A resin composition was produced.

2-3 Production of liquid epoxy resin composition [Composition Reference Example 3]
The inclusion compound obtained by the method of Synthesis Reference Example 1 was mixed with 0.4 g in terms of imidazole and 10 g of Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.) as a liquid epoxy resin to produce a liquid epoxy resin composition.

[Composition Example 3]
A liquid epoxy resin composition is produced in the same manner as in Composition Reference Example 3 except that the inclusion compound obtained by the method of Synthesis Example 1 is used instead of the inclusion compound obtained by the method of Synthesis Reference Example 1. did.

[Composition Example 4]
A liquid epoxy resin composition is produced in the same manner as in Reference Example 3 except that the inclusion compound obtained by the method of Synthesis Example 4 is used instead of the inclusion compound obtained by the method of Synthesis Reference Example 1. did.

[Composition Reference Example 4]
A liquid epoxy resin composition is produced in the same manner as in Composition Reference Example 3 except that the inclusion compound obtained by the method of Synthesis Reference Example 2 is used instead of the inclusion compound obtained by the method of Synthesis Reference Example 1. did.

[Test Example 1]
(Spiral flow test)
The epoxy resin compositions obtained by the methods of Composition Examples 1 and 2 and Composition Reference Examples 1 and 2 were tableted to form tablets. The lengths of these tablets were injection-molded for 3 minutes under the conditions of 175 ° C. and pressure 70 kgf / cm ² using an Archimedes spiral mold and a transfer molding machine. The spiral flow value is shown in Table 1 after measuring the initial value and the value after 7 days at 25 ° C.

  In the spiral flow test, the larger the value, the better the fluidity.

[Test Example 2]
(Geltime)
An appropriate amount of the epoxy resin composition obtained by the methods of Composition Examples 3 and 4 and Composition Reference Example 3 was placed on a hot plate at 175 ° C. with a metal spatula, stirred with a metal spatula, and sticky to the sample. Was measured, and the time when it became peeled off from the hot plate or the time when the tackiness disappeared was measured. The results are shown in Table 2.
The gel time is a time until the fluidity is lost when the encapsulant is heated at a constant temperature, and can be appropriately selected with respect to the curing characteristics. In order to show that it hardens early, so that gel time is short, especially in the case of a liquid epoxy resin, the one where gel time is short is preferable.

(Storage stability)
The epoxy resin compositions obtained by the methods of Composition Examples 3 and 4 and Composition Reference Example 3 were stored at 30 ° C. and visually observed, and when solidified, the measurement was terminated and storage stability was evaluated. The results are shown in Table 2.

According to the present invention, a 1: 2 clathrate compound of an aromatic carboxylic acid compound and an imidazole compound can be obtained with high purity.
In the present invention, since the 1: 2 clathrate compound can be produced with high purity, either the 1: 1 clathrate compound or the 1: 2 clathrate compound is used as a curing agent or a curing accelerator. The curable epoxy resin composition and the cured product thereof can be produced.

Claims (8)

Aromatic carboxylic acid compound (A) and formula (II)

(Wherein, _{R 2} is a hydrogen atom, C1 -C10 alkyl group, an aryl group, an arylalkyl group or cyanoethyl _group, R 3 to R ₅ is a hydrogen atom, a nitro group, a halogen atom, C1 to C20 alkyl group Represents a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or an acyl group of C1-C20. The portion with a broken line represents a single bond or a double bond. An inclusion compound containing the compound (B), wherein the molar ratio of (A) to (B) is 1: 2, and the inclusion compound contains (A) and (B) The clathrate compound or its composition which is 70 mol% to 100 mol% in the clathrate compound. The aromatic carboxylic acid compound is of formula (III)

(Wherein, n1 is .R ₆ is .n2 representing an integer of 1 to 4 representing an integer of 0 to 4 representing the C1~C6 alkyl group, a nitro group or a hydroxyl group.)
Or formula (IV)

(Wherein, m1 is .m2 representing an integer of 1 to 4 represent an integer of 0 to 2 .R ₇ is C1~C6 alkyl group, a nitro group, a hydroxyl group or the following formula

(Wherein q represents an integer of 1 or 2, * represents a bonding position). )
The clathrate compound or the composition thereof according to claim 1, wherein the clathrate compound or a composition thereof. Formula (IV) is converted to Formula (I)

(In the formula, R _1, C1 -C6 alkyl, C1 -C6 alkoxy group,. A nitro group or hydroxy group) inclusion compound according to claim 2, characterized in that the or compositions thereof. The inclusion compound or composition thereof according to claim 3, wherein the formula (I) is 5-hydroxyisophthalic acid. The inclusion compound or composition thereof according to any one of claims 1 to 4, wherein the formula (II) is 2-phenyl-4-methyl-5-hydroxymethylimidazole. The method for producing an inclusion compound or a composition thereof according to claim 1, wherein an aromatic carboxylic acid compound is added to the alcohol solution of the compound of formula (II). The method for producing an inclusion compound or a composition thereof according to claim 1, wherein an alcohol solution of an aromatic carboxylic acid compound is added to the compound of formula (II). A curable epoxy resin composition or a cured product thereof comprising the clathrate compound according to any one of claims 1 to 5 or a composition thereof and an epoxy resin.

Images