WO2011089874A1 - Clathrate and method for producing same - Google Patents
Clathrate and method for producing same Download PDFInfo
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- WO2011089874A1 WO2011089874A1 PCT/JP2011/000172 JP2011000172W WO2011089874A1 WO 2011089874 A1 WO2011089874 A1 WO 2011089874A1 JP 2011000172 W JP2011000172 W JP 2011000172W WO 2011089874 A1 WO2011089874 A1 WO 2011089874A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
Definitions
- the present invention relates to a novel clathrate compound and a method for producing the same, and in particular, an clathrate compound comprising an aromatic carboxylic acid compound and an imidazole compound useful as an epoxy resin curing catalyst and the like, 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.
- Epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties.
- an imidazole compound is used as a curing agent for curing such an epoxy resin.
- a mixed solution of an epoxy resin and an imidazole compound has a problem that the curing starts quickly and the one-component stability is extremely poor. .
- 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)) is used.
- TEP tetrakisphenol compound
- 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.
- R 1 represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a nitro group, or a hydroxyl group.
- R 2 represents a hydrogen atom, a C1-C10 alkyl group, an aryl group, an arylalkyl group or a cyanoethyl group
- R 3 to R 5 each independently represent a hydrogen atom, a nitro group, a halogen atom
- It represents a C1-C20 alkyl group which may have a substituent, a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group or a C1-C20 acyl group.
- An inclusion compound containing an imidazole compound represented by the formula was proposed and developed (Patent Document 3).
- the manufacturing method of the clathrate compound in Patent Document 3 is that after adding an isophthalic acid compound and an imidazole compound to a solvent, the mixture is subjected to heat treatment or heat reflux treatment with stirring as necessary, to cause precipitation.
- 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.
- Patent Document 3 does not specifically describe the inclusion compound of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole, but also describes it in the same patent document.
- 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole were reacted 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). The compound could not be produced with high purity.
- 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.
- 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.
- the known method produced 1: 2. It was found that 2 clathrate compounds could not be produced.
- 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.
- Aromatic carboxylic acid compound (A) and formula (II) are aromatic carboxylic acid compounds (A) and formula (II)
- R 2 represents a hydrogen atom, a C1-C10 alkyl group, an aryl group, an arylalkyl group or a cyanoethyl group
- R 3 -R 5 represent a hydrogen atom, a nitro group, a halogen atom, a C1-C20 alkyl group
- the portion with a broken line represents a single bond or a double bond.
- the aromatic carboxylic acid compound is represented by the formula (III)
- n1 represents an integer of 1 to 4.
- n2 represents an integer of 0 to 4.
- R 6 represents a C1 to C6 alkyl group, a nitro group, or a hydroxyl group.
- m1 represents an integer of 1 to 4.
- m2 represents an integer of 0 to 2.
- R 7 represents a C1-C6 alkyl group, a nitro group, a hydroxyl group, or a group represented by the following formula:
- R 1 represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a nitro group or a hydroxy group
- an inclusion compound or a composition thereof according to (2) above (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) above, which 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 comprising the clathrate compound according to any one of (1) to (5) or a composition thereof and an epoxy resin.
- 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. 3 is a diagram showing a 1 H-NMR chart of an inclusion compound obtained in Synthesis Example 3. 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. 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. 3 is a diagram showing a 1 H-NMR chart of an inclusion compound obtained in Synthesis Example 3.
- FIG. 4 is a diagram showing a 1 H-NMR chart of an inclusion compound obtained in Synthesis Example 3.
- FIG. 4 is a diagram showing a 1 H-NMR chart of an inclusion compound obtained in Synthesis 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.
- inclusion compound or 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)
- R 2 represents a hydrogen atom, a C1-C10 alkyl group, an aryl group, an arylalkyl group or a cyanoethyl group
- R 3 -R 5 represent a hydrogen atom, a nitro group, a halogen atom, a C1-C20 alkyl group
- 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.
- 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.
- 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.
- 5-hydroxyisophthalic acid is referred to as “HIPA” and 2-phenyl-4-methyl-5-hydroxymethylimidazole as “2P4MHZ”.
- 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.)
- 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 preferably 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.
- Carboxylic acid compound It does not restrict
- n1 represents an integer of 1 to 4.
- n2 represents an integer of 0 to 4.
- R 6 represents a C1 to C6 alkyl group, a nitro group, or a hydroxyl group.
- m1 represents an integer of 1 to 4.
- m2 represents an integer of 0 to 2.
- R 7 represents a C1-C6 alkyl group, a nitro group, a hydroxyl group, or a group represented by the following formula:
- the C1-C6 alkyl group of R 6 and R 7 includes a cycloalkyl group, and specifically includes a methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, 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-di
- R 1 represents a C1-C6 alkyl group, a 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.
- 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)
- 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, an n-hexyl group, a nonyl group, an i-nonyl group, a decyl group, and the like can be given.
- An aryl group means a monocyclic or 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 each independently represents a hydrogen atom, a nitro group, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C1-C20 group. Represents an acyl group.
- C1-C20 alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, 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.
- it is a C1-C10 alkyl group.
- aryl group and arylalkyl group include the same groups as those in R 2 .
- 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-methylhexadecano
- examples of the imidazole compound represented by the formula (II) include 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-hydroxymethyl Imidazole, 2-phenylimidazole or 2-phenyl-4,5-dihydroxymethylimidazole is preferred.
- Examples of the imidazoline compound represented by the formula (II) include 2-methyl imidazoline, 2-phenyl imidazoline, 2-undecyl imidazoline, 2-heptadecyl imidazoline, 2-ethyl imidazoline, 2-i-propyl imidazoline, 2,4- Examples thereof include dimethylimidazoline and 2-phenyl-4-methylimidazoline, and 2-methylimidazoline or 2-phenylimidazoline is preferable.
- 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
- 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.
- 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.
- the mixing ratio of the carboxylic acid compound and the imidazole compound is preferably 0.1 to 5.0 mol of the imidazole compound (guest) with respect to 1 mol of the carboxylic acid compound (host), and 0.5 to 3 More preferably, it is 0.0 mol.
- the alcohol solvent examples include lower alcohols such as methanol, ethanol and n-propanol, with methanol being preferred.
- the amount used is usually 0.5 to 50 times the weight of the carboxylic acid compound.
- 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.
- 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.
- 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.
- the mixing ratio of the carboxylic acid compound and the imidazole compound is preferably 0.1 to 5.0 mol of the imidazole compound (guest) with respect to 1 mol of the carboxylic acid compound (host), and 0.5 to 3 More preferably, it is 0.0 mol.
- the alcohol solvent examples 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.
- 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.
- 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.
- 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.
- the blending ratio of HIPA and 2P4MHZ in the method for producing a 1: 1 clathrate compound is preferably such that 2P4MHZ (guest) is 0.1 to 5.0 moles relative to 1 mole of HIPA (host). More preferably, it is from 5 to 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, with methanol being preferred.
- the amount used is usually 0.5 to 50 times the amount of HIPA.
- 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.
- the target compound is obtained by, for example, filtering and drying.
- 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.
- Epoxy resin Various conventionally known polyepoxy compounds can be used as the epoxy resin, for example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propane diglycidyl.
- Aromatic glycidyl ether 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, and
- 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.
- 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 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 methacrylate and lauryl methacrylate.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- curing agent or curing accelerator examples include the following compounds.
- 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
- alicyclic and heterocyclic amines examples 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.
- aromatic amines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline, ⁇ - And methylbenzylmethylamine.
- modified amines examples include epoxy compound-added polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-capped polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amineimide, boron trifluoride-piperidine. Complex, boron trifluoride-monoethylamine complex, and the like.
- imidazole compound examples 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 Dimethylimidazole, 2-ethyl-4-methyl
- imidazoline compound examples include 2-methylimidazoline and 2-phenylimidazoline.
- Examples of the amide compound include polyamide obtained by condensation of dimer acid and polyamine.
- ester compounds include active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids.
- 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.
- aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins
- phenol novolac 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.
- polyol-2-polymercaptan polysulfide
- 2- dimethylaminomethylphenol
- 2,4,6-tris dimethylaminomethyl
- 2,4,6-tris dimethylaminomethyl
- phenol tri-2- And ethyl hexyl hydrochloride 2- (dimethylaminomethylphenol), 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol tri-2- And ethyl hexyl hydrochloride.
- urea compounds, thiourea compounds, and Lewis acid compounds examples include butylated urea, butylated melamine, butylated thiourea, boron trifluoride, and the like.
- Examples of the phosphorus compound include organic phosphine compounds, for example, alkylphosphine such as ethylphosphine and butylphosphine, first phosphine such as phenylphosphine, dialkylphosphine such as dimethylphosphine and dipropylphosphine, diphenylphosphine, 2 phosphine; tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, and the like.
- alkylphosphine such as ethylphosphine and butylphosphine
- first phosphine such as phenylphosphine
- dialkylphosphine such as dimethylphosphine and dipropylphosphine
- diphenylphosphine diphenylphosphine
- 2 phosphine 2 phosphine
- 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 (anhydro trimellitate), glycerol tris (Anhydro trimellitate), methylcyclohexene tetracarboxylic acid anhydride, polyazeline acid anhydride and the like.
- Examples of the onium salt compound and the active silicon compound-aluminum complex include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triphenylsilanol-aluminum complexes, triphenylmethoxysilane-aluminum complexes, silyl peroxides- Examples thereof include aluminum complexes and triphenylsilanol-tris (salicylide) aluminum complexes.
- the curing agent or curing accelerator it is particularly preferable to use an amine compound, an imidazole compound, or a phenol compound.
- phenolic compounds it is more preferable to use a phenol resin curing agent.
- 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.
- additives include vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxy Propyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane Silane coupling agents such as N-phenyl- ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇
- 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 And 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.
- the epoxy resin composition of the present invention may contain other resins in addition to the epoxy resin.
- other resins include polyester resins, acrylic resins, silicone resins, polyurethane resins, and the like.
- 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.
- the epoxy cured resin forming composition can be produced by mixing the epoxy resin and the inclusion compound of the present invention or the composition thereof. 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.
- the heating temperature of the heat treatment is 60 ⁇ 250 ° C.
- composition Reference Example 1 Manufacture of epoxy resin composition 2-1 Manufacture of biphenyl type epoxy resin composition
- 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.
- 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.
- 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 of 191 to 201 (manufactured by Nippon Kayaku Co., Ltd.) as an o-cresol novolak epoxy resin, 18.886 g, 0.378 g of TOWAX (registered trademark) 131 (manufactured by Toa Kasei Co., Ltd.) as a mold 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.), 9.443 g of novolak phenol PSM-4261
- 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.
- 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.
- a 1: 2 clathrate compound of an aromatic carboxylic acid compound and an imidazole compound can be obtained with high purity.
- 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.
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Abstract
Description
本願は、2010年1月20日に出願された日本国特許出願第2010-10375号、2010年10月8日に出願された日本国特許出願第2010-228645号に対し優先権を主張し、その内容をここに援用する。 The present invention relates to a novel clathrate compound and a method for producing the same, and in particular, an clathrate compound comprising an aromatic carboxylic acid compound and an imidazole compound useful as an epoxy resin curing catalyst and the like, 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.
その後、5-ヒドロキシイソフタル酸と2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールの1:1包接化合物は高純度で製造することができた(特許文献4)が、1:2包接化合物を高純度で製造することはできなかった。 However, Patent Document 3 does not specifically describe the inclusion compound of 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole, but also describes it in the same patent document. When 5-hydroxyisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole were reacted 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). The compound could not be produced with high purity.
(1)芳香族カルボン酸化合物(A)及び式(II) That is, the present invention
(1) Aromatic carboxylic acid compound (A) and formula (II)
(2)芳香族カルボン酸化合物が、式(III) (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 -R 5 represent a hydrogen atom, a nitro group, a halogen atom, a C1-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 mol% to 100 mol% in the inclusion compound,
(2) The aromatic carboxylic acid compound is represented by the formula (III)
又は、式(IV) (In the formula, n1 represents an integer of 1 to 4. n2 represents an integer of 0 to 4. R 6 represents a C1 to C6 alkyl group, a nitro group, or a hydroxyl group.)
Or formula (IV)
で表される化合物であることを特徴とする前記(1)に記載の包接化合物又はその組成物、
(3)式(IV)が、式(I) (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)
(4)式(I)が5-ヒドロキシイソフタル酸であることを特徴とする前記(3)に記載の包接化合物又はその組成物、及び
(5)式(II)が2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールであることを特徴とする前記(1)~(4)のいずれかに記載の包接化合物又はその組成物に関する。 (Wherein R 1 represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a nitro group or a hydroxy group), or an inclusion compound or a composition thereof according to (2) above ,
(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) above, which is methyl-5-hydroxymethylimidazole.
(6)式(II)の化合物のアルコール液に芳香族カルボン酸化合物を添加することを特徴とする、前記(1)に記載の包接化合物又はその組成物の製造方法、
(7)式(II)の化合物に芳香族カルボン酸化合物のアルコール溶液を添加することを特徴とする、前記(1)に記載の包接化合物又はその組成物の製造方法に関し、
さらに、
(8)前記(1)~(5)のいずれかに記載の包接化合物又はその組成物と、エポキシ樹脂とを含有する硬化性エポキシ樹脂組成物又はその硬化物に関する。 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 comprising the clathrate compound according to any one of (1) to (5) or a composition thereof and an epoxy resin.
本発明の包接化合物又はその組成物は、芳香族カルボン酸化合物(以下、「カルボン酸化合物」と略す)をホスト化合物とし、式(II) (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)
略称として、5-ヒドロキシイソフタル酸は、「HIPA」、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールは「2P4MHZ」という。 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 abbreviations, 5-hydroxyisophthalic acid is referred to as “HIPA” and 2-phenyl-4-methyl-5-hydroxymethylimidazole as “2P4MHZ”.
1:2包接化合物の純度(%)=(2a/3-1)×100 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:
1: 2 purity of clathrate compound (%) = (2a / 3-1) × 100
芳香族カルボン酸化合物としては、特に制限されず、例えば次のものが例示できる。
安息香酸、2-メチル安息香酸、3-メチル安息香酸、4-メチル安息香酸、2-エチル安息香酸、3-エチル安息香酸、4-エチル安息香酸、2-n-プロピル安息香酸、3-n-プロピル安息香酸、4-n-プロピル安息香酸、2-ブチル安息香酸、3-ブチル安息香酸、4-ブチル安息香酸、2-i-プロピル安息香酸、3-i-プロピル安息香酸、4-i-プロピル安息香酸、2-i-ブチル安息香酸、3-i-ブチル安息香酸、4-i-ブチル安息香酸、2-ヒドロキシ安息香酸、3-ヒドロキシ安息香酸、4-ヒドロキシ安息香酸、2-ニトロ安息香酸、3-ニトロ安息香酸、4-ニトロ安息香酸、2-ニトロ安息香酸メチル、3-ニトロ安息香酸メチル、4-ニトロ安息香酸メチル、2-ニトロ安息香酸エチル、3-ニトロ安息香酸エチル、4-ニトロ安息香酸エチル、2-ニトロ安息香酸プロピル、3-ニトロ安息香酸プロピル、4-ニトロ安息香酸プロピル、2-ニトロ安息香酸ブチル、3-ニトロ安息香酸ブチル、4-ニトロ安息香酸ブチル、2,3-ジメチル安息香酸、2,4-ジメチル安息香酸、2,5-ジメチル安息香酸、2,6-ジメチル安息香酸、3,4-ジメチル安息香酸、3,5-ジメチル安息香酸、3,6-ジメチル安息香酸、4,5-ジメチル安息香酸、4,6-ジメチル安息香酸、2,3-ジエチル安息香酸、2,4-ジエチル安息香酸、2,5-ジエチル安息香酸、2,6-ジエチル安息香酸、3,4-ジエチル安息香酸、3,5-ジエチル安息香酸、3,6-ジエチル安息香酸、4,5-ジエチル安息香酸、4,6-ジエチル安息香酸、2,3-ジヒドロキシ安息香酸、2,4-ジヒドロキシ安息香酸、2,5-ジヒドロキシ安息香酸、2,6-ジヒドロキシ安息香酸、3,4-ジヒドロキシ安息香酸、3,5-ジヒドロキシ安息香酸、3,6-ジヒドロキシ安息香酸、4,5-ジヒドロキシ安息香酸、4,6-ジヒドロキシ安息香酸; (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;
これらの芳香族カルボン酸化合物は1種単独で用いても2種以上を併用してもよい。 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.
又は、式(IV) (In the formula, n1 represents an integer of 1 to 4. n2 represents an integer of 0 to 4. R 6 represents a C1 to C6 alkyl group, a nitro group, or a hydroxyl group.)
Or formula (IV)
R6、R7のC1~C6アルキル基はシクロアルキル基を包含し、具体的に、メチル基、エチル基、n-プロピル基、i-プロピル基、シクロプロピル基、n-ブチル基、i-ブチル基、s-ブチル基、t-ブチル基、シクロブチル基、シクロプロピルメチル基、n-ペンチル基、i-ペンチル基、2-メチルブチル基、ネオペンチル基、1-エチルプロピル基、n-ヘキシル基、i-ヘキシル基、4-メチルペンチル基、3-メチルペンチル基、2-メチルペンチル基、1-メチルペンチル基、3,3-ジメチルブチル基、2,2-ジメチルブチル基等が挙げられる。 (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, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, 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.
式中、R1は、C1~C6アルキル基、C1~C6アルコキシ基又はヒドロキシ基を表す。 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, a C1-C6 alkoxy group or a hydroxy group.
本発明において使用されるイミダゾール化合物は、式(II) (Imidazole compound)
The imidazole compound used in the present invention has the formula (II)
具体的には式(II)は、 It is an imidazole compound and an imidazoline compound represented by these.
Specifically, the formula (II) is
式中、R2は、水素原子、C1~C10アルキル基、アリール基、アリールアルキル基又はシアノエチル基を表し、水素原子であることが好ましい。 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.
実質的にカルボン酸化合物対イミダゾール化合物の1:2包接化合物又はその組成物は、次の方法等により得ることができる。
(1)イミダゾール化合物にカルボン酸化合物のアルコール溶液を添加する方法
(2)イミダゾール化合物のアルコール液にカルボン酸化合物を添加する方法 (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
イミダゾール化合物に、必要に応じて攪拌しながら、カルボン酸化合物のアルコール溶液を添加する。カルボン酸化合物のアルコール溶液の添加は、特に制限はないが、通常5~120分掛けて連続的又は分割して添加する。
カルボン酸化合物のアルコール溶液の添加後、必要に応じて室温にて0~5時間放置し、室温~40℃で0~5時間加熱又は0~5時間加熱還流させる。
カルボン酸化合物とイミダゾール化合物の配合割合としては、カルボン酸化合物(ホスト)1モルに対して、イミダゾール化合物(ゲスト)が、0.1~5.0モルであることが好ましく、0.5~3.0モルであることがより好ましい。 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.
The mixing ratio of the carboxylic acid compound and the imidazole compound is preferably 0.1 to 5.0 mol of the imidazole compound (guest) with respect to 1 mol of the carboxylic acid compound (host), and 0.5 to 3 More preferably, it is 0.0 mol.
加熱処理又は加熱還流処理後の工程は、例えば、単に加熱又は加熱還流処理を止めることにより固体化合物を析出させてもよいが、加熱した後、室温で一晩放置することが好ましい。固体化合物を析出させた後、例えばろ過して乾燥することにより、目的とする化合物が得られる。 Examples of the alcohol solvent include lower alcohols such as methanol, ethanol and n-propanol, with methanol being 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.
イミダゾール化合物をアルコールに懸濁もしくは溶解させた(アルコール懸濁液及びアルコール溶液をアルコール液という)後、必要に応じて攪拌しながらカルボン酸化合物を添加する。カルボン酸化合物の添加は、特に制限はないが、通常5~120分掛けて連続的又は分割して添加する。
カルボン酸化合物の添加後、必要に応じて室温にて0~5時間放置し、室温~40℃で0~5時間加熱又は0~5時間加熱還流させる。 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.
(HIPA対2P4MHZのモル比が1:1の包接化合物の製造方法)
実質的にHIPA対2P4MHZのモル比が1:1のみからなる包接化合物は、次の方法等により得ることができる。
HIPAをアルコールに溶解させた後、必要に応じて攪拌しながら2P4MHZを添加する。2P4MHZの添加は、特に制限はないが、通常5分以上、好ましくは5分~120分かけて連続的又は分割して添加する。
2P4MHZの添加後、必要に応じて室温にて0~5時間放置し、室温~40℃で0~5時間加熱又は0~5時間加熱還流させる。 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.
本発明の包接化合物又はその組成物は、エポキシ樹脂硬化剤又は硬化促進剤として、エポキシ樹脂と混合して、たとえば、半導体封止剤として使用することができる。
半導体封止剤などとして使用する硬化エポキシ樹脂組成物は、エポキシ樹脂、本発明の包接化合物、及び、必要に応じて、その他の添加剤を含有する。 (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.
エポキシ樹脂としては、従来公知の各種ポリエポキシ化合物が使用でき、例えば、ビス(4-ヒドロキシフェニル)プロパンジグリシジルエーテル、ビス(4-ヒドロキシ-3,5-ジブロモフェニル)プロパンジグリシジルエーテル、ビス(4-ヒドロキシフェニル)エタンジグリシジルエーテル、ビス(4-ヒドロキシフェニル)メタンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、フロログリシノールトリグリシジルエーテル、トリヒドロキシビフェニルトリグリシジルエーテル、テトラグリシジルベンゾフェノン、ビスレゾルシノールテトラグリシジルエーテル、テトラメチルビスフェノールAジグリシジルエーテル、ビスフェノールCジグリシジルエーテル、ビスフェノールヘキサフルオロプロパンジグリシジルエーテル、1,3-ビス〔1-(2,3-エポキシプロポキシ)-1-トリフルオロメチル-2,2,2-トリフルオロエチル〕ベンゼン、1,4-ビス〔1-(2,3-エポキシプロポキシ)-1-トリフルオロメチル-2,2,2-トリフルオロメチル〕ベンゼン、4,4’-ビス(2,3-エポキシプロポキシ)オクタフルオロビフェニル、フェノールノボラック型ビスエポキシ化合物等の芳香族系グリシジルエーテル化合物、アリサイクリックジエポキシアセタール、アリサイクリックジエポキシアジペート、アリサイクリックジエポキシカルボキシレート、ビニルシクロヘキセンジオキシド等の脂環式ポリエポキシ化合物、ジグリシジルフタレート、ジグリシジルテトラヒドロフタレート、ジグリシジルヘキサヒドロフタレート、ジメチルグリシジルフタレート、ジメチルグリシジルヘキサヒドロフタレート、ジグリシジル-p-オキシベンゾエート、ジグリシジルシクロペンタン-1,3-ジカルボキシレート、ダイマー酸グリシジルエステル等のグリシジルエステル化合物、ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジルアミノフェノール、テトラグリシジルジアミノジフェニルメタン、ジグリシジルトリブロモアニリン等のグリシジルアミン化合物、ジグリシジルヒダントイン、グリシジルグリシドオキシアルキルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物等を挙げることができる。 1) Epoxy resin Various conventionally known polyepoxy compounds can be used as the epoxy resin, for example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propane diglycidyl. 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 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, and diglycidyltribromoaniline, and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate.
本発明のエポキシ樹脂組成物は、上記包接化合物及びエポキシ樹脂を含んでいればよく、また、包接化合物及びエポキシ樹脂に加えて無機充填剤を含む、エポキシ樹脂組成物であってもよい。 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.
本発明のエポキシ樹脂組成物において、上記包接化合物に加え、硬化促進剤もしくは硬化剤をさらに含んでいても良い。 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.
脂肪族アミン類としては、例えば、エチレンジアミン、トリメチレンジアミン、トリエチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジプロピレンジアミン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、トリメチルヘキサメチレンジアミン、ペンタンジアミン、ビス(2-ジメチルアミノエチル)エーテル、ペンタメチルジエチレントリアミン、アルキル-t-モノアミン、1,4-ジアザビシクロ(2,2,2)オクタン(トリエチレンジアミン)、N,N,N’,N’-テトラメチルヘキサメチレンジアミン、N,N,N’,N’-テトラメチルプロピレンジアミン、N,N,N’,N’-テトラメチルエチレンジアミン、N,N-ジメチルシクロヘキシルアミン、ジブチルアミノプロピルアミン、ジメチルアミノエトキシエトキシエタノール、トリエタノールアミン、ジメチルアミノヘキサノール等が挙げられる。 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.
本発明のエポキシ樹脂組成物には前述のもののほか、必要に応じて可塑剤、有機溶剤、反応性希釈剤、増量剤、充填剤、補強剤、顔料、難燃化剤、増粘剤及び離型剤など種々の添加剤を配合できる。その他の添加剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリエトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、N-β(アミノエチル)γ-アミノプロピルトリメトキシシラン、N-β(アミノエチル)γ-アミノプロピルトリエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、N-フェニル-γ-アミノプロピルトリエトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルトリエトキシシラン等のシランカップリング剤;重炭酸カルシウム、軽質炭酸カルシウム、天然シリカ、合成シリカ、溶融シリカ、カオリン、クレー、酸化チタン、硫酸バリウム、酸化亜鉛、水酸化アルミニウム、水酸化マグネシウム、タルク、マイカ、ウォラスナイト、チタン酸カリウム、ホウ酸アルミニウム、セピオライト、ゾノトライト等の充填剤;NBR、ポリブタジエン、クロロプレンゴム、シリコーン、架橋NBR、架橋BR、アクリル系、コアシェルアクリル、ウレタンゴム、ポリエステルエラストマー、官能基含有液状NBR、液状ポリブタジエン、液状ポリエステル、液状ポリサルファイド、変性シリコーン、ウレタンプレポリマー等のエラストマー変性剤; 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, 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;
エポキシ樹脂と本発明の包接化合物又はその組成物の配合割合は、エポキシ樹脂のエポキシ環1モルに対して、包接化合物又はその組成物中のイミダゾール化合物を0.01~1.0モル含有することが好ましく、0.1~1.0モル含有することがより好ましく、0.3~1.0モル含有することがさらに好ましい。 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.
なお、以下の実施例において、1HNMRはDMSO-d6もしくはMeOH-d4を測定溶媒として用い、25℃で測定した。 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.
[合成実施例1]
フラスコに2P4MHZ20.67g(109.8mmol)を入れた後、攪拌しながら、HIPA20g(109.8mmol)をメタノール170mlに溶解して得た液の半分を添加した。メタノール11mLで洗い、室温で0.5時間放置後、攪拌しながら残りのHIPAメタノール溶液を添加し、メタノール11mLで洗い、室温で0.5時間放置後、3時間加熱還流した。その後、室温で一晩放置した後、ろ過・真空乾燥することによって生成物28.89gを得た(収率71%)。得られた生成物を1HNMR、X線回折および熱分析(DSC)で分析したところ、HIPA:2P4MHZが1:2の包接化合物の結晶であった。また、1:2包接化合物の純度は、91%であった。得られた包接化合物の温度変化による熱分析(DSC)チャートを図1に示す。 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 hours, and then the remaining HIPA methanol solution was added with stirring. 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.
フラスコに2P4MHZ20.67g(109.8mmol)とメタノール130mlを投入し混合して得たアルコール液に、攪拌しながら、HIPA10g(54.9mmol)を20分かけて添加した。室温にて0.5時間放置後、3時間加熱還流した。その後、室温で一晩放置した後、ろ過・真空乾燥することによって生成物29.91gを得た(収率97.5%)。得られた生成物を1HNMR、X線回折および熱分析(DSC)で分析したところ、HIPA:2P4MHZが1:2の包接化合物の結晶であった。また、1:2包接化合物の純度は、97%であった。得られた包接化合物の温度変化による熱分析(DSC)チャート及び1HNMRチャートを図2-1及び図2-2に示す。 [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 according to temperature change of the resulting clathrate are shown in FIGS. 2-1 and 2-2.
フラスコに2P4MHZ20.67g(109.8mmol)を入れた後、攪拌しながら、HIPA10g(54.9mmol)をメタノール130mlに溶解して得た液を15分かけて添加した。室温で0.5時間放置後、3時間加熱還流した。その後、室温で一晩放置した後、ろ過・真空乾燥することによって生成物29.74gを得た(収率97%)。得られた生成物を1HNMR、X線回折および熱分析(DSC)で分析したところ、HIPA:2P4MHZが1:2の包接化合物の結晶であった。また、1:2包接化合物の純度は、99%であった。得られた包接化合物の温度変化による熱分析(DSC)チャート及び1HNMRチャートを図3-1及び図3-2に示す。 [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 1 HNMR chart according to temperature change of the resulting clathrate are shown in FIGS. 3-1 and 3-2.
2P4MHZの代わりに無置換イミダゾール(以下、Imと呼ぶ)7.48g(109.8mmol)を用いること以外は、合成実施例2と同様に、HIPA:Imが1:2の包接化合物を得た。また、1:2包接化合物の純度は77%であった。得られた包接化合物の温度変化による熱分析(DSC)チャート及び1HNMRチャートを図4-1及び図4-2に示す。 [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 according to temperature change of the resulting clathrate are shown in FIGS. 4-1 and 4-2.
フラスコにHIPA20g(109.8mmol)とメタノール126mlを投入し混合して得た溶液に、攪拌しながら、2P4MHZ20.67g(109.8mmol)を15分かけて添加した。室温にて2時間放置後、3時間加熱還流した。その後、室温で一晩放置した後、ろ過・真空乾燥することによって生成物39.56gを得た(収率97.3%)。得られた生成物を1HNMR、X線回折および熱分析(DSC)で分析したところ、HIPA:2P4MHZが1:1の包接化合物の結晶であった。また、1:2包接化合物の純度は、0%であった。得られた包接化合物の温度変化による熱分析(DSC)チャートを図5に示す。 [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.
2P4MHZの代わりにlm7.48g(109.8mmol)を用いること以外は、合成参考例1と同様に、HIPA:Imが1:1の包接化合物を得た。 [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.
フラスコにHIPA36.43g(200mmol)、2P4MHZ37.65g(200mmol)及びメタノール230mlを投入し、攪拌して、3時間加熱還流を行った。その後、室温で一晩放置した後、ろ過・真空乾燥することによって生成物64.41gを得た(収率87.2%)。得られた生成物を1HNMR、X線回折および熱分析(DSC)で分析したところ、実施例1及び2と異なるデータを示したので、HIPA:2P4MHZが1:1の包接化合物と1:2の包接化合物が混ざった結晶と判断した。また、1:2包接化合物の純度は、18%であった。得られた包接化合物の温度変化による熱分析(DSC)チャートを図6に示す。 [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.
2-1 ビフェニル型エポキシ樹脂組成物の製造
[組成物参考例1]
合成参考例1の方法で得られた包接化合物をイミダゾール換算で0.249g、ビフェニル型エポキシ樹脂としてYX4000H(三菱化学株式会社製)12.445g、離型剤としてTOWAX(登録商標)131(東亜化成株式会社製)0.249g、フィラーとしてFB-940球状シリカ(電気化学工業株式会社製)179.97g、シランカップリング剤としてLS2940(信越化学工業株式会社製)0.383g、硬化剤としてノボラックフェノールPSM-4261 OH当量103(群栄化学工業株式会社製)6.701gを、100℃で5分間加熱混練し、冷却後、粉砕してビフェニル型エポキシ樹脂組成物を製造した。 2 Manufacture of epoxy resin composition 2-1 Manufacture 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.
合成参考例1の方法で得られた包接化合物に代えて合成実施例1の方法で得られた包接化合物を用いること以外は、組成物参考例1と同様に、ビフェニル型エポキシ樹脂組成物を製造した。 [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.
[組成物参考例2]
合成参考例1の方法で得られた包接化合物をイミダゾール換算で0.378g、o-クレゾールノボラックエポキシ樹脂としてEOCN-1020-55 エポキシ当量191~201(日本化薬株式会社製)18.886g、離型剤としてTOWAX(登録商標)131(東亜化成株式会社製)0.378g、フィラーとしてFB-940球状シリカ(電気化学工業株式会社製)169.97g、シランカップリング剤としてLS-2940(信越化学社製)0.944g、硬化剤としてノボラックフェノールPSM-4261 OH当量103(群栄化学工業株式会社製)9.443gを、100℃で5分間加熱混練し、冷却後、粉砕してビフェニル型エポキシ樹脂組成物を製造した 。 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 of 191 to 201 (manufactured by Nippon Kayaku Co., Ltd.) as an o-cresol novolak epoxy resin, 18.886 g, 0.378 g of TOWAX (registered trademark) 131 (manufactured by Toa Kasei Co., Ltd.) as a mold 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.), 9.443 g of novolak phenol PSM-4261 OH equivalent 103 (manufactured by Gunei Chemical Industry Co., Ltd.) as a curing agent was heated and kneaded at 100 ° C. for 5 minutes, cooled, pulverized and biphenyl type An epoxy resin composition was produced.
合成参考例1の方法で得られた包接化合物に代えて合成実施例1の方法で得られた包接化合物を用いること以外は、組成物参考例2と同様に、o-クレゾールノボラック型エポキシ樹脂組成物を製造した。 [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.
[組成物参考例3]
合成参考例1の方法で得られた包接化合物をイミダゾール換算で0.4g、液状エポキシ樹脂としてエポトートYD-128(東都化成株式会社製)10gを混合し、液状エポキシ樹脂組成物を製造した。 2-3 Production of liquid epoxy resin composition [Composition Reference Example 3]
A clathrate 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.
合成参考例1の方法で得られた包接化合物に代えて合成実施例1の方法で得られた包接化合物を用いる以外は、組成物参考例3と同様に、液状エポキシ樹脂組成物を製造した。 [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.
合成参考例1の方法で得られた包接化合物に代えて合成実施例4の方法で得られた包接化合物を用いる以外は、組成物参考例3と同様に、液状エポキシ樹脂組成物を製造した。 [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.
合成参考例1の方法で得られた包接化合物に代えて合成参考例2の方法で得られた包接化合物を用いる以外は、組成物参考例3と同様に、液状エポキシ樹脂組成物を製造した。 [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.
(スパイラルフロー試験)
組成物実施例1及び2、組成物参考例1及び2の方法で得られたエポキシ樹脂組成物をそれぞれ打錠し、錠剤を成型した。これらの錠剤を、アルキメデススパイラル金型とトランスファー成形機を用いて、175℃、圧力70Kgf/cm2の条件で3分間射出成形したものの長さを測定した。スパイラルフロー値は初期値及び25℃で7日間経過後の値を測定し、第1表に示す。 [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
(ゲルタイム)
組成物実施例3及び4、組成物参考例3の方法で得られたエポキシ樹脂組成物の適量を金属製ヘラで175℃の熱板に置き、金属製ヘラを使ってかき混ぜ、試料に粘着性がなくなり、熱板から剥がれるようになった時間または粘着性がなくなった時間を測定した。結果を第2表に示す。
ゲルタイムは封止材を一定温度で加熱したとき、流動性を失うまでの時間であり、硬化特性に関し、適宜選択できる。ゲルタイムが短いほど早く固まることを示すため、特に液状エポキシ樹脂の場合は、ゲルタイムが短いほうが好ましい。 [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.
組成物実施例3及び4、組成物参考例3の方法で得られたエポキシ樹脂組成物を30℃保存、目視観察を行い、固化した時点で測定終了とし、保存安定性を評価した。結果を第2表に示す。 (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.
また、本発明において、1:2包接化合物を高純度で製造することができるようになったため、1:1包接化合物と1:2包接化合物のいずれかを硬化剤又は硬化促進剤として含有する、硬化性エポキシ樹脂組成物及びその硬化物を製造することができるようになった。 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)
- 芳香族カルボン酸化合物(A)及び式(II)
- 芳香族カルボン酸化合物が、式(III)
又は、式(IV)
で表される化合物であることを特徴とする請求項1に記載の包接化合物又はその組成物。 The aromatic carboxylic acid compound is of formula (III)
Or formula (IV)
The clathrate compound or the composition thereof according to claim 1, wherein the clathrate compound or a composition thereof. - 式(IV)が、式(I)
- 式(I)が5-ヒドロキシイソフタル酸であることを特徴とする請求項3に記載の包接化合物又はその組成物。 The inclusion compound or composition thereof according to claim 3, wherein the formula (I) is 5-hydroxyisophthalic acid.
- 式(II)が2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールであることを特徴とする請求項1~4のいずれかに記載の包接化合物又はその組成物。 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.
- 式(II)の化合物のアルコール液に芳香族カルボン酸化合物を添加することを特徴とする、請求項1に記載の包接化合物又はその組成物の製造方法。 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).
- 式(II)の化合物に芳香族カルボン酸化合物のアルコール溶液を添加することを特徴とする、請求項1に記載の包接化合物又はその組成物の製造方法。 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).
- 請求項1~5のいずれかに記載の包接化合物又はその組成物と、エポキシ樹脂とを含有する硬化性エポキシ樹脂組成物又はその硬化物。 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.
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JP2011550838A JP5536108B2 (en) | 2010-01-20 | 2011-01-14 | Inclusion compound and method for producing the same |
CN201180006305.8A CN102725273B (en) | 2010-01-20 | 2011-01-14 | Inclusion compound and manufacture method thereof |
BR112012016151A BR112012016151A2 (en) | 2010-01-20 | 2011-01-14 | clathrate, method for producing a clathrate or composition thereof, and curable epoxy resin composition or a cured product thereof |
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Cited By (4)
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WO2012035755A1 (en) * | 2010-09-15 | 2012-03-22 | 日本曹達株式会社 | Liquid curable epoxy resin composition and adhesive agent containing same |
JP2013136702A (en) * | 2011-12-28 | 2013-07-11 | Namics Corp | Liquid sealing material |
JP2013177514A (en) * | 2012-02-28 | 2013-09-09 | Furukawa Electric Co Ltd:The | Adhesive film, tape for processing wafer, and method for producing the adhesive film |
CN106589828A (en) * | 2016-12-22 | 2017-04-26 | 科化新材料泰州有限公司 | Environment-friendly epoxy resin composition and preparation method thereof |
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US10266642B2 (en) * | 2014-09-08 | 2019-04-23 | Nippon Soda Co., Ltd. | Crystal polymorphism of inclusion compound and method for producing same, and curable resin composition |
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JP2002179597A (en) * | 2000-12-11 | 2002-06-26 | Nippon Soda Co Ltd | Method for producing molecular compound |
JP2007191450A (en) * | 2006-01-20 | 2007-08-02 | Nippon Soda Co Ltd | Method for producing inclusion compound by slurry method |
WO2008075427A1 (en) * | 2006-12-21 | 2008-06-26 | Nippon Soda Co., Ltd. | Clathrate compound, curing catalyst, composition for forming cured resin, and cured resin |
WO2009037862A1 (en) * | 2007-09-21 | 2009-03-26 | Nippon Soda Co., Ltd. | Inclusion complex containing epoxy resin composition for semiconductor encapsulation |
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2011
- 2011-01-14 WO PCT/JP2011/000172 patent/WO2011089874A1/en active Application Filing
- 2011-01-14 JP JP2011550838A patent/JP5536108B2/en not_active Expired - Fee Related
- 2011-01-14 CN CN201180006305.8A patent/CN102725273B/en not_active Expired - Fee Related
- 2011-01-14 BR BR112012016151A patent/BR112012016151A2/en not_active Application Discontinuation
- 2011-01-18 TW TW100101845A patent/TWI525073B/en not_active IP Right Cessation
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JP2002179597A (en) * | 2000-12-11 | 2002-06-26 | Nippon Soda Co Ltd | Method for producing molecular compound |
JP2007191450A (en) * | 2006-01-20 | 2007-08-02 | Nippon Soda Co Ltd | Method for producing inclusion compound by slurry method |
WO2008075427A1 (en) * | 2006-12-21 | 2008-06-26 | Nippon Soda Co., Ltd. | Clathrate compound, curing catalyst, composition for forming cured resin, and cured resin |
WO2009037862A1 (en) * | 2007-09-21 | 2009-03-26 | Nippon Soda Co., Ltd. | Inclusion complex containing epoxy resin composition for semiconductor encapsulation |
Cited By (6)
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WO2012035755A1 (en) * | 2010-09-15 | 2012-03-22 | 日本曹達株式会社 | Liquid curable epoxy resin composition and adhesive agent containing same |
EP2617750A1 (en) * | 2010-09-15 | 2013-07-24 | Nippon Soda Co., Ltd. | Liquid curable epoxy resin composition and adhesive agent containing same |
EP2617750A4 (en) * | 2010-09-15 | 2014-02-19 | Nippon Soda Co | Liquid curable epoxy resin composition and adhesive agent containing same |
JP2013136702A (en) * | 2011-12-28 | 2013-07-11 | Namics Corp | Liquid sealing material |
JP2013177514A (en) * | 2012-02-28 | 2013-09-09 | Furukawa Electric Co Ltd:The | Adhesive film, tape for processing wafer, and method for producing the adhesive film |
CN106589828A (en) * | 2016-12-22 | 2017-04-26 | 科化新材料泰州有限公司 | Environment-friendly epoxy resin composition and preparation method thereof |
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JP5536108B2 (en) | 2014-07-02 |
CN102725273A (en) | 2012-10-10 |
JPWO2011089874A1 (en) | 2013-05-23 |
TWI525073B (en) | 2016-03-11 |
CN102725273B (en) | 2016-02-17 |
TW201139358A (en) | 2011-11-16 |
BR112012016151A2 (en) | 2015-09-15 |
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