WO2015125674A1 - Diepoxy compound and composition containing said compound - Google Patents

Diepoxy compound and composition containing said compound Download PDF

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Publication number
WO2015125674A1
WO2015125674A1 PCT/JP2015/053683 JP2015053683W WO2015125674A1 WO 2015125674 A1 WO2015125674 A1 WO 2015125674A1 JP 2015053683 W JP2015053683 W JP 2015053683W WO 2015125674 A1 WO2015125674 A1 WO 2015125674A1
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Prior art keywords
epoxypropoxy
cyclohexyl
compound
alumina
phenyl
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PCT/JP2015/053683
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French (fr)
Japanese (ja)
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武史 原
義彦 岩永
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住友化学株式会社
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Publication of WO2015125674A1 publication Critical patent/WO2015125674A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium

Definitions

  • the present invention relates to a diepoxy compound and a composition containing the compound.
  • Epoxy cured products obtained by curing diepoxy compounds are widely used industrially because they exhibit excellent mechanical and electrical properties in addition to good heat resistance and moisture resistance.
  • a cured product obtained by curing a diepoxy compound having a mesogenic skeleton and a curing agent has been reported to exhibit high thermal conductivity.
  • an epoxy resin having a biphenyl skeleton and a curing agent are cured.
  • Patent Document 1 and Patent Document 2 describe that the cured product obtained in this way is excellent in thermal conductivity.
  • the conventional diepoxy compound having a mesogen skeleton has a high melting point and has a problem that a high temperature is required for production of a prepreg and the like.
  • a diepoxy compound represented by the formula (1) (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer of 1 to 3).
  • a dihydroxy compound represented by the formula (2) (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer of 1 to 3).
  • a composition comprising a diepoxy compound represented by formula (1) and a curing agent.
  • Alumina includes alumina particles A having D50 of 2 ⁇ m or more and 100 ⁇ m or less, alumina particles B having D50 of 1 ⁇ m or more and 10 ⁇ m or less, and alumina particles C having D50 of 0.01 ⁇ m or more and 5 ⁇ m or less [4 ]
  • D50 means a particle diameter of 50% cumulative volume from the fine particle side of the weight cumulative particle size distribution.
  • the diepoxy compound of the present invention is a compound represented by formula (1) (hereinafter sometimes referred to as compound (1)).
  • compound (1) each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • Q represents an oxygen atom or a methylene group
  • n represents an integer of 1 to 3
  • Examples of the alkyl group having 1 to 3 carbon atoms represented by R 1 to R 12 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R 1 to R 12 may be the same as or different from each other.
  • R 1 to R 12 are preferably the combinations described in the following (i), more preferably the combinations described in any of the following (ii) to (iv), and further preferably the combinations described in the following (ii). It is a combination.
  • R 1 to R 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 to R 12 are hydrogen atoms.
  • R 1 to R 12 are hydrogen atoms.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and R 2 to R 12 are hydrogen atoms.
  • R 3 is an alkyl group having 1 to 3 carbon atoms, and R 1 , R 2 and R 4 to R 12 are hydrogen atoms.
  • Q is preferably a methylene group.
  • n is preferably 1.
  • the compound (1) is preferably a compound represented by the following formula (1 ′). (Wherein R 1 to R 4 represent the same meaning as described above.)
  • the melting point of compound (1) is usually 70 to 125 ° C.
  • Compound (1) is usually a dihydroxy compound represented by the following formula (2) (hereinafter sometimes referred to as compound (2)) and an epihalohydrin represented by the following formula (3) in the presence of an ammonium salt and an inorganic base. Obtained by reacting the compound (2) with the compound represented by the following formula (4) in the presence of a base to obtain a diallylated product represented by the formula (5). Manufactured by a method of oxidizing a diallylated product with an oxidizing agent. (In the formula, R 1 to R 12 , Q and n represent the same meaning as described above. X 1 and X 2 represent a halogen atom.)
  • the halogen atom represented by X 1 and X 2 is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom.
  • the compound (2) is preferably a compound represented by the following formula (2 ′). (Wherein R 1 to R 4 represent the same meaning as described above.)
  • Compound (2) is usually a carboxylic acid compound represented by the following formula (6) and an alcohol represented by the following formula (7) in the presence of an acid catalyst (hereinafter sometimes referred to as alcohol (7)). And the ester compound represented by the following formula (8) and the alcohol (7) in the presence of a Lewis acid catalyst.
  • R 1 to R 12 , Q and n represent the same meaning as described above.
  • R 13 represents an alkyl group having 1 to 6 carbon atoms.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
  • a linear or branched alkyl group such as a cyclic alkyl group such as a cyclopropyl group, a 2,2-dimethylcyclopropyl group, a cyclopentyl group, and a cyclohexyl group, preferably a methyl group or an ethyl group
  • the alcohol (7) is preferably a compound represented by the following formula (7 ′).
  • Alcohol (7 ′) may be a commercially available product or may be produced according to the method described in Japanese Patent No. 3930669.
  • the composition containing the compound (1) and a curing agent contains at least one compound (1) and at least one curing agent, Two or more kinds may be used in combination.
  • the present composition may further contain a solvent. Including a solvent facilitates the preparation of the composition.
  • the solvent include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, ester solvents such as butyl acetate, and propylene glycol monomethyl ether.
  • the glycol solvent is preferably a ketone solvent, more preferably methyl isobutyl ketone.
  • Examples of the method for producing the present composition include a method of mixing the compound (1) and a curing agent in a solvent.
  • the curing agent is one having at least one functional group capable of reacting with the epoxy group of the compound (1), or a curing catalyst exhibiting a catalytic action in the curing reaction of the compound (1).
  • Specific examples include an amine curing agent having an amino group as the functional group, a phenol curing agent having a hydroxyl group as the functional group, an acid anhydride curing agent having an acid anhydride structure as the functional group, and a curing catalyst.
  • An amine curing agent, a phenol curing agent, and a curing catalyst are preferable.
  • amine curing agent examples include aliphatic polyamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine (that is, aliphatic carbonization having 2 to 20 carbon atoms).
  • aromatic polyvalent amines and dicyandiamide Preferred are aromatic polyvalent amines and dicyandiamide, and more preferred are 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene, p-phenylenediamine and dicyandiamide. is there.
  • the phenol curing agent examples include a phenol resin, a phenol aralkyl resin (having a phenylene skeleton, a diphenylene skeleton, etc.), a naphthol aralkyl resin, a polyoxystyrene resin, and the like.
  • the phenol resin examples include aniline-modified resole resin, resol type phenol resin such as dimethyl ether resole resin, phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, novolac type phenol resin such as nonylphenol novolac resin, and dicyclopentadiene modified.
  • Special phenol resins such as phenol resin, terpene-modified phenol resin, and triphenol methane type resin can be used.
  • the polyoxystyrene resin examples include poly (p-oxystyrene).
  • Examples of the acid anhydride curing agent include maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, and 5- (2,5-dicarboxylic acid anhydride).
  • curing catalyst examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and benzyldimethylamine.
  • the amount of the curing agent used is appropriately selected according to the type of curing agent used.
  • the amount of the curing agent used is usually such that the molar number of the functional group that can react with the epoxy group of the compound (1) that the curing agent has is 0.5 to 1 with respect to 1 mol of the epoxy group of the compound (1). It is adjusted to be 5 mol, preferably 0.9 to 1.1 mol.
  • the composition may further contain other epoxy compounds.
  • Other epoxy compounds include bisphenol A type epoxy compounds, orthocresol type epoxy compounds, biphenol diglycidyl ether, 4,4′-bis (3,4-epoxybuten-1-yloxy) phenyl benzoate, naphthalene diglycidyl ether, ⁇ -methylstilbene-4,4′-diglycidyl ether, 4- ⁇ 4- (2,3-epoxypropoxy) phenyl ⁇ cyclohexyl 4- (2,3-epoxypropoxy) benzoate, 4- ⁇ 4- (2, 3-epoxypropoxy) phenyl ⁇ cyclohexyl 4- (2,3-epoxypropoxy) -2-methylbenzoate, 4- ⁇ 4- (2,3-epoxypropoxy) phenyl ⁇ cyclohexyl 4- (2,3-epoxypropoxy) -3-methylbenzoate, 4- ⁇ 4- ( 2,3-epoxypropoxy) phenyl ⁇
  • the present composition contains 4- ⁇ 4- (2,3-epoxypropoxy) phenyl ⁇ cyclohexyl 4- (2,3-epoxypropoxy) benzoate. It is preferable to include.
  • the content of the other epoxy compound with respect to 100 parts by mass of the compound (1) is preferably 5 to 1900 parts by mass, more preferably 20 to 900 parts by mass, and further preferably 20 to 400 parts by mass. Part by mass.
  • the content of the other epoxy compound is 5 to 1900 parts by mass, the prepreg tends to be produced at a low temperature, and the obtained cured product tends to have high thermal conductivity.
  • this composition contains another epoxy compound
  • curing agent contained in this composition has a hardening
  • the number of moles of the functional group capable of reacting with the epoxy group is adjusted to 0.5 to 1.5 mol, preferably 0.9 to 1.1 mol.
  • the composition preferably comprises alumina.
  • the cured product of the present composition containing alumina tends to have better thermal conductivity.
  • the composition preferably also includes a solvent.
  • the content of alumina in the present composition is usually 75 to 95 parts by mass, preferably 83 to 93 parts by mass with respect to 100 parts by mass of the active ingredient contained in the present composition.
  • the alumina content is 75 parts by mass or more, the thermal conductivity of the resulting cured product is further improved, and when it is 95 parts by mass or less, the composition is preferably molded.
  • the active ingredient which this composition contains is components other than the solvent which this composition contains.
  • the alumina is preferably particulate.
  • the particulate alumina preferably comprises alumina particles A having a D50 of 2 ⁇ m or more and 100 ⁇ m or less, alumina particles B having a D50 of 1 ⁇ m or more and 10 ⁇ m or less, and alumina particles C having a D50 of 0.01 ⁇ m or more and 5 ⁇ m or less.
  • D50 is a particle diameter of 50% cumulative volume from the fine particle side of the weight cumulative particle size distribution, and the particle diameter can be measured by a laser diffraction method.
  • the content of alumina particles A contained in alumina is preferably 50 to 90% by volume, and the content of alumina particles B is preferably 5 to 40% by volume,
  • the content of alumina particles C is preferably 1 to 30% by volume.
  • the content of alumina particles A is more preferably 60 to 90% by volume, the content of alumina particles B is more preferably 10 to 30% by volume, and the content of alumina particles C is more preferably 5 to 20% by volume. %.
  • Such alumina can be prepared by appropriately mixing commercially available alumina particles having various average particle sizes.
  • the content ratio of alumina contained in the cured product obtained by curing the present composition is preferably 50 to 80% by volume, more preferably 60 to 74% by volume.
  • the present composition may further contain various additives.
  • Additives include curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, and 2-phenylimidazole; couplings such as ⁇ -glycidoxypropyltrimethoxysilane Agents; Colorants such as carbon black; Low stress components such as silicone oil and silicone rubber; Mold release agents such as natural wax, synthetic wax, higher fatty acid, metal salt of higher fatty acid and paraffin; Antioxidant; Examples thereof include silica such as silica powder, fused spherical silica powder, crystalline silica powder and secondary agglomerated silica powder or powder thereof; titanium white; aluminum hydroxide; talc; clay; mica and glass fiber. Content of the various additives in this composition is suitably adjusted in the grade which does not reduce desired performance, such as melting
  • a method for producing a cured product obtained by curing the composition is a method of curing the composition by heating it to a predetermined temperature as it is; melting and heating the composition The composition is then poured into a mold and the mold is further heated to form; the composition is melted; the resulting melt is poured into a preheated mold and cured; the composition is partially A method of curing, pulverizing the partially cured product obtained, filling the obtained powder into a mold, and melt-molding the filled powder; and dissolving the composition in a solvent as necessary and stirring the part Examples include a method of curing and casting the obtained solution, followed by drying and removing the solvent by ventilation drying or the like, and heating for a predetermined time while applying pressure with a press machine or the like as necessary.
  • the composition contains alumina
  • the composition is heated to a predetermined temperature as it is to cure; the composition is heated and melted and poured into a mold, and the mold is further heated to form.
  • a cured product is produced by a method of filling a mold and melt-molding the filled powder.
  • the present composition containing a solvent is used as it is, or further diluted with a solvent and applied or impregnated on a substrate, and then the obtained substrate is heated to semi-cur the compound (1) in the substrate.
  • a prepreg can be obtained.
  • a laminated board can also be obtained by laminating a plurality of the obtained prepregs and pressing and heating them with a press or the like.
  • the base material used for producing the prepreg include woven or nonwoven fabrics of inorganic fibers such as glass fibers and carbon fibers, and woven or nonwoven fabrics of organic fibers such as polyester.
  • the heating temperature is preferably 70 to 130 ° C, more preferably 70 to 125 ° C, and further preferably 70 to 120 ° C.
  • This composition is preferable because curing proceeds at a temperature of about 70 ° C. to 130 ° C., so that the prepreg can be easily produced and the productivity becomes high.
  • Example 1 Production Example 1 of dihydroxy compound (2)
  • Production example of 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenyl) propanoate represented by the formula (2-1) (hereinafter sometimes referred to as dihydroxy compound (2-1)).
  • dihydroxy compound (2-1) 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenyl) propanoate represented by the formula (2-1)
  • a reaction vessel equipped with a rectifying column 139 mmol of methyl 3- (4-hydroxyphenyl) propionate, 139 mmol of 4- (4-hydroxycyclohexyl) phenol, 2.8 mmol of dibutyltin oxide and 125 g of 4-chlorotoluene were mixed. .
  • the resulting mixture was stirred for 10 hours while being heated to reflux, and then cooled to room temperature.
  • the alcohol produced as the reaction progressed was removed from the reaction vessel using a rectification column. Then, the crude product was obtained by isolate
  • Example 2 Production Example 2 of dihydroxy compound (2)
  • Production example of 4- (4-hydroxyphenyl) cyclohexyl 3- (3-methyl-4-hydroxyphenyl) propanoate represented by formula (2-2) (hereinafter sometimes referred to as dihydroxy compound (2-2)) .
  • dihydroxy compound (2-2) 4- (4-hydroxyphenyl) cyclohexyl 3- (3-methyl-4-hydroxyphenyl) propanoate represented by formula (2-2) (hereinafter sometimes referred to as dihydroxy compound (2-2)) .
  • a reaction vessel equipped with a rectifying column 86 mmol of methyl 3- (3-methyl-4-hydroxyphenyl) propionate, 86 mmol of 4- (4-hydroxycyclohexyl) phenol, 1.7 mmol of dibutyltin oxide and 4-chlorotoluene 84 g was mixed.
  • the resulting mixture was stirred for 10 hours while being heated to reflux, and then cooled to room temperature.
  • the alcohol produced as the reaction progressed was removed from the reaction vessel using a rectification column. Then, the crude product was obtained by isolate
  • Example 3 Production Example 3 of dihydroxy compound (2)
  • Production example of 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenoxy) acetate represented by the formula (2-3) (hereinafter sometimes referred to as dihydroxy compound (2-3)).
  • a reaction vessel equipped with a rectifying column 121 mmol of methyl 3- (4-hydroxyphenoxy) acetate, 121 mmol of 4- (4-hydroxycyclohexyl) phenol, 2.0 mmol of dibutyltin oxide and 110 g of 4-chlorotoluene were mixed. The resulting mixture was stirred for 10 hours while being heated to reflux, and then cooled to room temperature.
  • the alcohol produced as the reaction progressed was removed from the reaction vessel using a rectification column. Then, the crude product was obtained by isolate
  • Example 4 Production Example 1 of diepoxy compound (1)] 4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenyl] propanoate represented by formula (1-1) (hereinafter referred to as diepoxy compound (1-1) ))).
  • Dihydroxy compound (2-1) 44 mmol, tetrabutylammonium bromide 8.8 mmol) and epichlorohydrin 1321 mmol were stirred and mixed at 70 ° C. for 12 hours, and then cooled to 25 ° C.
  • Example 5 Production Example 2 of diepoxy compound (1)] 4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenyl] propanoate represented by the formula (1-2) (hereinafter referred to as diepoxy compound) (1-2))). 44 mmol of the dihydroxy compound (2-2), 8.5 mmol of tetrabutylammonium bromide and 1693 mmol of epichlorohydrin were stirred and mixed at 70 ° C. for 12 hours, and then cooled to 25 ° C.
  • Example 6 Production Example 3 of diepoxy compound (1)] 4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenoxy] acetate (hereinafter referred to as diepoxy compound (1-3) represented by formula (1-3) ))).
  • diepoxy compound (1-3) represented by formula (1-3)
  • Dihydroxy compound (2-3) 50 mmol, tetrabutylammonium bromide 9.9 mmol) and epichlorohydrin 1493 mmol were stirred and mixed at 60 ° C. for 10 hours, and then cooled to 25 ° C.
  • Example 7 Production Example 1 of composition and cured product thereof] 100 parts by mass of white crystals containing the diepoxy compound (1-1) obtained in Example 4, 16 parts by mass of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.), and 1068 parts by mass of alumina powder (Sumitomo Chemical) The mixture was adjusted by mixing three types of ⁇ -alumina powder manufactured by Co., Ltd.
  • Alumina powder A1 (D50: 18 ⁇ ) / Alumina powder B1 (D50: 3 ⁇ m) / Alumina powder C1 (D50: 0.4 ⁇ m) ⁇ mass ratio> 749/149/128, ⁇ volume ratio> 74/14/12), 530 parts by mass of methyl isobutyl ketone, and 60 parts by mass of N, N-dimethylformamide.
  • a product (1) was prepared. The composition (1) was applied on a polyethylene terephthalate (PET) film substrate using an applicator so that the thickness was 350 ⁇ m. The PET film coated with the composition (1) was dried at room temperature for 1 hour, further heated and dried at 120 ° C.
  • PET polyethylene terephthalate
  • the obtained prepreg sheet was sandwiched between aluminum foils having a thickness of 40 ⁇ m, and vacuum press molding (press temperature: 130 ° C., degree of vacuum: 1 kPa, press pressure: 6 MPa, treatment time: 20 minutes) was performed, and then over 40 minutes.
  • the press temperature was raised to 180 ° C.
  • the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 320 ⁇ m.
  • the thermal conductivity of the obtained cured product was measured using a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH, it was 7.2 W / (m ⁇ K).
  • the density of the cured product obtained by curing the composition containing the diepoxy compound (1-1) and 1,5-diaminonaphthalene and not the alumina powder is 1.2 g / cm 3 , and the density of the alumina powder is 3
  • the content ratio of the alumina powder in the obtained cured product was calculated as .97 g / cm 3 , and the content ratio of the alumina powder in the cured product was 74% by volume.
  • composition (2) 3 types of ⁇ -alumina powder manufactured by Sumitomo Chemical Co., Ltd.
  • Alumina powder A1 (D50: 18 ⁇ ) / alumina powder B1 (D50: 3 ⁇ m) / alumina powder C1 (D50: 0.4 ⁇ m) ⁇ mass ratio> 848/160/132, ⁇ volume ratio> 74/14/12), and methyl isobutyl ketone 530 mass Part and 60 parts by mass of N, N-dimethylformamide were mixed to prepare composition (2).
  • the composition (2) was applied on a polyethylene terephthalate (PET) film so as to have a thickness of 350 ⁇ m using an applicator.
  • PET film coated with the composition (2) was dried at room temperature for 1 hour and further heated and dried at 120 ° C. for 10 minutes. However, the epoxy monomer was not sufficiently melted and a semi-cured product was not obtained.
  • composition (2) was applied onto a polyethylene terephthalate (PET) film substrate using an applicator so that the thickness was 350 ⁇ m.
  • PET polyethylene terephthalate
  • the PET film coated with the composition (2) was dried at room temperature for 1 hour, further heated and dried at 140 ° C. for 10 minutes, semi-cured, and after the solvent was distilled off, the PET film was peeled off to obtain a prepreg sheet. .
  • the obtained prepreg sheet was sandwiched between aluminum foils having a thickness of 40 ⁇ m, and vacuum press molding (press temperature: 140 ° C., vacuum degree: 1 kPa, press pressure: 6 MPa, treatment time: 20 minutes) was performed, and then, for 40 minutes.
  • the press temperature was raised to 180 ° C.
  • the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 398 ⁇ m.
  • the thermal conductivity of the obtained cured product was measured using a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH, it was 6.9 W / (m ⁇ K).
  • the diepoxy compound of the present invention has a low melting point, a prepreg could be produced at a lower temperature. Furthermore, the hardened
  • the diepoxy compound of the present invention has a low melting point, and a cured product obtained from the diepoxy compound is useful because it has excellent thermal conductivity.

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Abstract

Provided is a diepoxy compound represented by formula (1). (In the formula, R1 to R12 each independently represent a hydrogen atom or an alkyl group having 1-3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer from 1 to 3.)

Description

ジエポキシ化合物及び、該化合物を含む組成物DIEPOXY COMPOUND AND COMPOSITION CONTAINING THE COMPOUND
　本発明は、ジエポキシ化合物及び、該化合物を含む組成物等に関する。 The present invention relates to a diepoxy compound and a composition containing the compound.
　ジエポキシ化合物を硬化させて得られるエポキシ硬化物は、良好な耐熱性及び耐湿性に加えて、機械的及び電気的に優れた特性を示すことから工業的に広く利用されている。
　中でも、メソゲン骨格を有するジエポキシ化合物と硬化剤とを硬化させて得られる硬化物は、高い熱伝導性を示すことが報告されており、例えば、ビフェニル骨格を有するエポキシ樹脂と硬化剤とを硬化させて得られる硬化物が、熱伝導性に優れることが特許文献１および特許文献２に記載されている。 Epoxy cured products obtained by curing diepoxy compounds are widely used industrially because they exhibit excellent mechanical and electrical properties in addition to good heat resistance and moisture resistance.
Among them, a cured product obtained by curing a diepoxy compound having a mesogenic skeleton and a curing agent has been reported to exhibit high thermal conductivity. For example, an epoxy resin having a biphenyl skeleton and a curing agent are cured. Patent Document 1 and Patent Document 2 describe that the cured product obtained in this way is excellent in thermal conductivity.
特許第２８７４０８９号Japanese Patent No. 2874089 特開２０１０－２４１９８８号JP 2010-241988
　しかしながら、メソゲン骨格を有する従来のジエポキシ化合物は、融点が高く、プリプレグ等の製造に高温を必要とするという問題があった。 However, the conventional diepoxy compound having a mesogen skeleton has a high melting point and has a problem that a high temperature is required for production of a prepreg and the like.
　本発明は、以下の発明を含む。
［１］　式（１）で表わされるジエポキシ化合物。
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ１～Ｒ１２はそれぞれ独立して、水素原子又は炭素数１～３のアルキル基を表わし、Ｑは酸素原子またはメチレン基を表す。ｎは１～３の整数を表す。）
［２］　式（２）で表わされるジヒドロキシ化合物。
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ１～Ｒ１２はそれぞれ独立して、水素原子又は炭素数１～３のアルキル基を表わし、Ｑは酸素原子またはメチレン基を表す。ｎは１～３の整数を表す。）
［３］　式（１）で表わされるジエポキシ化合物及び硬化剤を含む組成物。
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ１～Ｒ１２はそれぞれ独立して、水素原子又は炭素数１～３のアルキル基を表わし、Ｑは酸素原子またはメチレン基を表す。）
［４］　さらに、アルミナを含む［３］に記載の組成物。
［５］　アルミナが、２μｍ以上１００μｍ以下のＤ５０を有するアルミナ粒子Ａと、１μｍ以上１０μｍ以下のＤ５０を有するアルミナ粒子Ｂと、０．０１μｍ以上５μｍ以下のＤ５０を有するアルミナ粒子Ｃとを含む［４］に記載の組成物。Ｄ５０とは、重量累積粒度分布の微粒子側からの累積体積５０％の粒子径を意味する。
［６］　アルミナの体積を１００体積％としたとき、アルミナに含まれる、アルミナ粒子Ａの含有量が５０～９０体積％であり、アルミナ粒子Ｂの含有量が５～４０体積％であり、アルミナ粒子Ｃの含有量が１～３０体積％である［５］に記載の組成物。
［７］　［３］～［６］のいずれか記載の組成物を基材に塗布もしくは含浸した後、半硬化して得られるプリプレグ。
［８］　［３］～［６］のいずれか記載の組成物を硬化して得られる硬化物。
［９］　アルミナを５０～８０体積％含有することを特徴とする［８］記載の硬化物。 The present invention includes the following inventions.
[1] A diepoxy compound represented by the formula (1).
Figure JPOXMLDOC01-appb-C000004
 (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer of 1 to 3).
[2] A dihydroxy compound represented by the formula (2).
Figure JPOXMLDOC01-appb-C000005
 (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer of 1 to 3).
[3] A composition comprising a diepoxy compound represented by formula (1) and a curing agent.
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q represents an oxygen atom or a methylene group.)
[4] The composition according to [3], further comprising alumina.
[5] Alumina includes alumina particles A having D50 of 2 μm or more and 100 μm or less, alumina particles B having D50 of 1 μm or more and 10 μm or less, and alumina particles C having D50 of 0.01 μm or more and 5 μm or less [4 ] The composition of description. D50 means a particle diameter of 50% cumulative volume from the fine particle side of the weight cumulative particle size distribution.
[6] When the volume of alumina is 100% by volume, the content of alumina particles A contained in alumina is 50 to 90% by volume, and the content of alumina particles B is 5 to 40% by volume. The composition according to [5], wherein the content of particles C is 1 to 30% by volume.
[7] A prepreg obtained by applying or impregnating a composition according to any one of [3] to [6] to a substrate and then semi-curing it.
[8] A cured product obtained by curing the composition according to any one of [3] to [6].
[9] The cured product according to [8], containing 50 to 80% by volume of alumina.
　本発明によれば、熱伝導性に優れる硬化物を与える、融点が低いジエポキシ化合物を提供することができる。 According to the present invention, it is possible to provide a diepoxy compound having a low melting point that gives a cured product having excellent thermal conductivity.
　本発明のジエポキシ化合物は、式（１）で表される化合物（以下、化合物（１）ということがある。）である。
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ１～Ｒ１２はそれぞれ独立して、水素原子又は炭素数１～３のアルキル基を表わし、Ｑは酸素原子またはメチレン基を表す。ｎは１～３の整数を表す。） The diepoxy compound of the present invention is a compound represented by formula (1) (hereinafter sometimes referred to as compound (1)).
Figure JPOXMLDOC01-appb-C000007
 (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer of 1 to 3).
　Ｒ１～Ｒ１２で表される炭素数１～３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基及び、イソプロピル基が挙げられる。Ｒ１～Ｒ１２は、互いに、同一であっても、異なっていてもよい。 Examples of the alkyl group having 1 to 3 carbon atoms represented by R 1 to R 12 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R 1 to R 12 may be the same as or different from each other.
　Ｒ１～Ｒ１２は好ましくは下記（ｉ）に記載の組み合わせであり、より好ましくは下記（ｉｉ）～（ｉｖ）のいずれかに記載の組み合わせであり、さらに好ましくは下記（ｉｉ）に記載の組み合わせである。
（ｉ）Ｒ１～Ｒ４がそれぞれ独立して、水素原子又は炭素数１～３のアルキル基であり、Ｒ５～Ｒ１２が水素原子である。
（ｉｉ）Ｒ１～Ｒ１２が水素原子である。
（ｉｉｉ）Ｒ１が炭素数１～３のアルキル基であり、Ｒ２～Ｒ１２が水素原子である。
（ｉｖ）Ｒ３が炭素数１～３のアルキル基であり、Ｒ１、Ｒ２及び、Ｒ４～Ｒ１２が水素原子である。 R 1 to R 12 are preferably the combinations described in the following (i), more preferably the combinations described in any of the following (ii) to (iv), and further preferably the combinations described in the following (ii). It is a combination.
(I) R 1 to R 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 to R 12 are hydrogen atoms.
(Ii) R 1 to R 12 are hydrogen atoms.
(Iii) R 1 is an alkyl group having 1 to 3 carbon atoms, and R 2 to R 12 are hydrogen atoms.
(Iv) R 3 is an alkyl group having 1 to 3 carbon atoms, and R 1 , R 2 and R 4 to R 12 are hydrogen atoms.
　Ｑは、好ましくはメチレン基である。
　ｎは、好ましくは１である。 Q is preferably a methylene group.
n is preferably 1.
　化合物（１）は、好ましくは下記式（１’）で表わされる化合物である。
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ１～Ｒ４は前記と同じ意味を表わす。） The compound (1) is preferably a compound represented by the following formula (1 ′).
Figure JPOXMLDOC01-appb-C000008
 (Wherein R 1 to R 4 represent the same meaning as described above.)
　化合物（１）としては、具体的には、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェニル］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［２－メチル－４－（２，３－エポキシプロポキシ）フェニル］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－メチル－４－（２，３－エポキシプロポキシ）フェニル］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－エチル－４－（２，３－エポキシプロポキシ）フェニル］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－イソプロピル－４－（２，３－エポキシプロポキシ）フェニル］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３，５－ジメチル－４－（２，３－エポキシプロポキシ）フェニル］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェノキシ］アセテート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［２－メチル－４－（２，３－エポキシプロポキシ）フェノキシ］アセテート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－メチル－４－（２，３－エポキシプロポキシ）フェノキシ］アセテート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－エチル－４－（２，３－エポキシプロポキシ）フェノキシ］アセテート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－イソプロピル－４－（２，３－エポキシプロポキシ）フェノキシ］アセテート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３，５－ジメチル－４－（２，３－エポキシプロポキシ）フェノキシ］アセテート； As the compound (1), specifically,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenyl] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [2-methyl-4- (2,3-epoxypropoxy) phenyl] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenyl] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-ethyl-4- (2,3-epoxypropoxy) phenyl] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-isopropyl-4- (2,3-epoxypropoxy) phenyl] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3,5-dimethyl-4- (2,3-epoxypropoxy) phenyl] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenoxy] acetate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [2-methyl-4- (2,3-epoxypropoxy) phenoxy] acetate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenoxy] acetate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-ethyl-4- (2,3-epoxypropoxy) phenoxy] acetate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-isopropyl-4- (2,3-epoxypropoxy) phenoxy] acetate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3,5-dimethyl-4- (2,3-epoxypropoxy) phenoxy] acetate;
　４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェニル］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［２－メチル－４－（２，３－エポキシプロポキシ）フェニル］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－メチル－４－（２，３－エポキシプロポキシ）フェニル］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－エチル－４－（２，３－エポキシプロポキシ）フェニル］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－イソプロピル－４－（２，３－エポキシプロポキシ）フェニル］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３，５－ジメチル－４－（２，３－エポキシプロポキシ）フェニル］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェノキシ］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［２－メチル－４－（２，３－エポキシプロポキシ）フェノキシ］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－メチル－４－（２，３－エポキシプロポキシ）フェノキシ］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－エチル－４－（２，３－エポキシプロポキシ）フェノキシ］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－イソプロピル－４－（２，３－エポキシプロポキシ）フェノキシ］プロパノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３，５－ジメチル－４－（２，３－エポキシプロポキシ）フェノキシ］プロパノエート； 4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenyl] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [2-methyl-4- (2,3-epoxypropoxy) phenyl] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenyl] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-ethyl-4- (2,3-epoxypropoxy) phenyl] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-isopropyl-4- (2,3-epoxypropoxy) phenyl] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3,5-dimethyl-4- (2,3-epoxypropoxy) phenyl] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenoxy] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [2-methyl-4- (2,3-epoxypropoxy) phenoxy] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenoxy] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-ethyl-4- (2,3-epoxypropoxy) phenoxy] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-isopropyl-4- (2,3-epoxypropoxy) phenoxy] propanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3,5-dimethyl-4- (2,3-epoxypropoxy) phenoxy] propanoate;
　４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェニル］ペンタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［２－メチル－４－（２，３－エポキシプロポキシ）フェニル］ペンタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－メチル－４－（２，３－エポキシプロポキシ）フェニル］ペンタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－エチル－４－（２，３－エポキシプロポキシ）フェニル］ペンタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－イソプロピル－４－（２，３－エポキシプロポキシ）フェニル］ペンタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３，５－ジメチル－４－（２，３－エポキシプロポキシ）フェニル］ペンタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェノキシ］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［２－メチル－４－（２，３－エポキシプロポキシ）フェノキシ］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－メチル－４－（２，３－エポキシプロポキシ）フェノキシ］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－エチル－４－（２，３－エポキシプロポキシ）フェノキシ］ブタノエート、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－イソプロピル－４－（２，３－エポキシプロポキシ）フェノキシ］ブタノエート、及び、
４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３，５－ジメチル－４－（２，３－エポキシプロポキシ）フェノキシ］ブタノエート等が挙げられる。 4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenyl] pentanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [2-methyl-4- (2,3-epoxypropoxy) phenyl] pentanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenyl] pentanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-ethyl-4- (2,3-epoxypropoxy) phenyl] pentanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-isopropyl-4- (2,3-epoxypropoxy) phenyl] pentanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3,5-dimethyl-4- (2,3-epoxypropoxy) phenyl] pentanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenoxy] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [2-methyl-4- (2,3-epoxypropoxy) phenoxy] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenoxy] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-ethyl-4- (2,3-epoxypropoxy) phenoxy] butanoate,
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-isopropyl-4- (2,3-epoxypropoxy) phenoxy] butanoate, and
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3,5-dimethyl-4- (2,3-epoxypropoxy) phenoxy] butanoate and the like.
　化合物（１）の融点は、通常７０～１２５℃である。 The melting point of compound (1) is usually 70 to 125 ° C.
　化合物（１）は通常、下記式（２）で表わされるジヒドロキシ化合物（以下、化合物（２）ということがある。）と、下記式（３）表わされるエピハロヒドリンとを、アンモニウム塩及び無機塩基の存在下で反応させる方法、又は、塩基の存在下で化合物（２）と下記式（４）で表わされる化合物とを反応させて、式（５）で表わされるジアリル化物を得た後、得られたジアリル化物を酸化剤で酸化する方法等で製造される。
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ１～Ｒ１２、Ｑ及びｎは前記と同じ意味を表わす。Ｘ１及びＸ２はハロゲン原子を表す。） Compound (1) is usually a dihydroxy compound represented by the following formula (2) (hereinafter sometimes referred to as compound (2)) and an epihalohydrin represented by the following formula (3) in the presence of an ammonium salt and an inorganic base. Obtained by reacting the compound (2) with the compound represented by the following formula (4) in the presence of a base to obtain a diallylated product represented by the formula (5). Manufactured by a method of oxidizing a diallylated product with an oxidizing agent.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 (In the formula, R 1 to R 12 , Q and n represent the same meaning as described above. X 1 and X 2 represent a halogen atom.)
　Ｘ１及びＸ２で表されるハロゲン原子は、好ましくは塩素原子、臭素原子又は、ヨウ素原子であり、より好ましくは塩素原子である。 The halogen atom represented by X 1 and X 2 is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom.
　化合物（２）は、好ましくは下記式（２’）で表わされる化合物である。
Figure JPOXMLDOC01-appb-C000013
 （式中、Ｒ１～Ｒ４は前記と同じ意味を表わす。） The compound (2) is preferably a compound represented by the following formula (2 ′).
Figure JPOXMLDOC01-appb-C000013
 (Wherein R 1 to R 4 represent the same meaning as described above.)
　化合物（２）としては、具体的には、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェニル）プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（２－メチル－４－ヒドロキシフェニル）プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－メチル－４－ヒドロキシフェニル）プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－エチル－４－ヒドロキシフェニル）プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－イソプロピル－４－ヒドロキシフェニル）プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３，５－ジメチル－４－ヒドロキシフェニル）プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェノキシ）　アセテート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（２－メチル－４－ヒドロキシフェノキシ）　アセテート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－メチル－４－ヒドロキシフェノキシ）　アセテート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－エチル－４－ヒドロキシフェノキシ）　アセテート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－イソプロピル－４－ヒドロキシフェノキシ）　アセテート及び、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３，５－ジメチル－４－ヒドロキシフェノキシ）　アセテート； As the compound (2), specifically, 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenyl) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (2-methyl-4-hydroxy) Phenyl) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-methyl-4-hydroxyphenyl) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-ethyl-4-hydroxyphenyl) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-isopropyl-4-hydroxyphenyl) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3,5-dimethyl-4-hydroxyphenyl) propanoate, 4- ( -Hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenoxy) acetate, 4- (4-hydroxyphenyl) cyclohexyl 3- (2-methyl-4-hydroxyphenoxy) acetate, 4- (4-hydroxyphenyl) cyclohexyl 3- ( 3-methyl-4-hydroxyphenoxy) acetate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-ethyl-4-hydroxyphenoxy) acetate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-isopropyl- 4-hydroxyphenoxy) acetate and 4- (4-hydroxyphenyl) cyclohexyl 3- (3,5-dimethyl-4-hydroxyphenoxy) acetate;
　４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェニル）ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（２－メチル－４－ヒドロキシフェニル）ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－メチル－４－ヒドロキシフェニル）ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－エチル－４－ヒドロキシフェニル）ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－イソプロピル－４－ヒドロキシフェニル）ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３，５－ジメチル－４－ヒドロキシフェニル）ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェノキシ）　プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（２－メチル－４－ヒドロキシフェノキシ）　プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－メチル－４－ヒドロキシフェノキシ）　プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－エチル－４－ヒドロキシフェノキシ）　プロパノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－イソプロピル－４－ヒドロキシフェノキシ）　プロパノエート及び、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３，５－ジメチル－４－ヒドロキシフェノキシ）　プロパノエート； 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenyl) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (2-methyl-4-hydroxyphenyl) butanoate, 4- (4-hydroxyphenyl) Cyclohexyl 3- (3-methyl-4-hydroxyphenyl) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-ethyl-4-hydroxyphenyl) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- ( 3-Isopropyl-4-hydroxyphenyl) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3,5-dimethyl-4-hydroxyphenyl) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- ( -Hydroxyphenoxy) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (2-methyl-4-hydroxyphenoxy) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-methyl-4-hydroxyphenoxy) Propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-ethyl-4-hydroxyphenoxy) propanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-isopropyl-4-hydroxyphenoxy) propanoate and 4 -(4-hydroxyphenyl) cyclohexyl 3- (3,5-dimethyl-4-hydroxyphenoxy) propanoate;
　４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェニル）ペンタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（２－メチル－４－ヒドロキシフェニル）ペンタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－メチル－４－ヒドロキシフェニル）ペンタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－エチル－４－ヒドロキシフェニル）ペンタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－イソプロピル－４－ヒドロキシフェニル）ペンタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３，５－ジメチル－４－ヒドロキシフェニル）ペンタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェノキシ）　ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（２－メチル－４－ヒドロキシフェノキシ）　ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－メチル－４－ヒドロキシフェノキシ）　ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－エチル－４－ヒドロキシフェノキシ）　ブタノエート、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－イソプロピル－４－ヒドロキシフェノキシ）　ブタノエート及び、４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３，５－ジメチル－４－ヒドロキシフェノキシ）　ブタノエート等が挙げられる。 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenyl) pentanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (2-methyl-4-hydroxyphenyl) pentanoate, 4- (4-hydroxyphenyl) Cyclohexyl 3- (3-methyl-4-hydroxyphenyl) pentanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-ethyl-4-hydroxyphenyl) pentanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- ( 3-Isopropyl-4-hydroxyphenyl) pentanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3,5-dimethyl-4-hydroxyphenyl) pentanoate, 4- (4-hydroxyphenyl) cyclohex 3- (4-hydroxyphenoxy) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (2-methyl-4-hydroxyphenoxy) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-methyl- 4-hydroxyphenoxy) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-ethyl-4-hydroxyphenoxy) butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3-isopropyl-4-hydroxyphenoxy) ) Butanoate, 4- (4-hydroxyphenyl) cyclohexyl 3- (3,5-dimethyl-4-hydroxyphenoxy) butanoate and the like.
　化合物（２）は通常、酸触媒の存在下、下記式（６）で表されるカルボン酸化合物と、下記式（７）で表されるアルコール（以下、アルコール（７）ということがある。）とを脱水縮合させる方法、又は、ルイス酸触媒の存在下、下記式（８）で表されるエステル化合物と、アルコール（７）とをエステル交換反応させる方法等で製造される。
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒ１～Ｒ１２、Ｑ及びｎは前記と同じ意味を表わす。Ｒ１３は炭素数１～６のアルキル基を表わす。） Compound (2) is usually a carboxylic acid compound represented by the following formula (6) and an alcohol represented by the following formula (7) in the presence of an acid catalyst (hereinafter sometimes referred to as alcohol (7)). And the ester compound represented by the following formula (8) and the alcohol (7) in the presence of a Lewis acid catalyst.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
 (In the formula, R 1 to R 12 , Q and n represent the same meaning as described above. R 13 represents an alkyl group having 1 to 6 carbon atoms.)
　Ｒ１３で表される炭素数１～６のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基等の直鎖状又は分岐状のアルキル基、及び、シクロプロピル基、２，２－ジメチルシクロプロピル基、シクロペンチル基、シクロヘキシル基等の環状のアルキル基が挙げられ、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基及び、ブチル基であり、より好ましくはメチル基である。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. And a linear or branched alkyl group such as a cyclic alkyl group such as a cyclopropyl group, a 2,2-dimethylcyclopropyl group, a cyclopentyl group, and a cyclohexyl group, preferably a methyl group or an ethyl group , A propyl group, an isopropyl group and a butyl group, more preferably a methyl group.
　アルコール（７）は、好ましくは下記式（７’）で表される化合物である。
Figure JPOXMLDOC01-appb-C000017
 　アルコール（７’）は、市販品でもよいし、特許第３９３０６６９号公報に記載の方法に従って製造したものでもよい。 The alcohol (7) is preferably a compound represented by the following formula (7 ′).
Figure JPOXMLDOC01-appb-C000017
 Alcohol (7 ′) may be a commercially available product or may be produced according to the method described in Japanese Patent No. 3930669.
　化合物（１）及び硬化剤を含む組成物（以下、本組成物ということがある。）は、少なくとも１種の化合物（１）と、少なくとも１種の硬化剤と、を含むものであり、それぞれ２種以上を組み合わせて用いてもよい。本組成物は、さらに、溶媒を含んでいてもよい。溶媒を含むことにより、本組成物の調製が容易になる。
　当該溶媒としては、メチルエチルケトン、メチルイソブチルケトン等のケトン溶媒、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチルピロリドン等の非プロトン性極性溶媒、酢酸ブチル等のエステル溶媒、プロピレングリゴールモノメチルエーテル等のグリコール溶媒等が挙げられ、好ましくは、ケトン溶媒であり、より好ましくはメチルイソブチルケトンである。 The composition containing the compound (1) and a curing agent (hereinafter sometimes referred to as the present composition) contains at least one compound (1) and at least one curing agent, Two or more kinds may be used in combination. The present composition may further contain a solvent. Including a solvent facilitates the preparation of the composition.
Examples of the solvent include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, ester solvents such as butyl acetate, and propylene glycol monomethyl ether. The glycol solvent is preferably a ketone solvent, more preferably methyl isobutyl ketone.
　本組成物の製造方法としては、例えば、化合物（１）と硬化剤とを溶媒中で混合する方法を挙げることができる。 Examples of the method for producing the present composition include a method of mixing the compound (1) and a curing agent in a solvent.
　硬化剤とは、化合物（１）が有するエポキシ基と反応し得る官能基を少なくとも１個有するもの、又は、化合物（１）の硬化反応において触媒作用を示す硬化触媒である。具体的には、前記官能基としてアミノ基を有するアミン硬化剤、前記官能基として水酸基を有するフェノール硬化剤、前記官能基として酸無水物構造を有する酸無水物硬化剤及び、硬化触媒が挙げられる。好ましくは、アミン硬化剤、フェノール硬化剤及び、硬化触媒である。 The curing agent is one having at least one functional group capable of reacting with the epoxy group of the compound (1), or a curing catalyst exhibiting a catalytic action in the curing reaction of the compound (1). Specific examples include an amine curing agent having an amino group as the functional group, a phenol curing agent having a hydroxyl group as the functional group, an acid anhydride curing agent having an acid anhydride structure as the functional group, and a curing catalyst. . An amine curing agent, a phenol curing agent, and a curing catalyst are preferable.
　アミン硬化剤としては、エチレンジアミン、トリメチレンジアミン、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等の炭素数２～２０の脂肪族多価アミン（すなわち、炭素数２～２０の脂肪族炭化水素に含まれる水素原子の一部がアミノ基に置換された化合物）、ｐ－キシレンジアミン、ｍ－キシレンジアミン、１，５－ジアミノナフタレン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルエタン、４，４’－ジアミノジフェニルプロパン、４，４’－ジアミノジフェニルエーテル、１，１－ビス（４－アミノフェニル）シクロヘキサン、４，４’－ジアミノジフェニルスルホン、ビス（４－アミノフェニル）フェニルメタン等の芳香族多価アミン（すなわち、芳香族炭化水素基を有する炭素数６～２０の炭化水素における芳香族炭化水素基に含まれる水素原子の一部がアミノ基に置換された化合物）、４，４’－ジアミノジシクロヘキサン、１，３－ビス（アミノメチル）シクロヘキサン等の脂環式多価アミン（すなわち、脂環式炭化水素基を有する炭素数５～２０の炭化水素における脂環式炭化水素基に含まれる水素原子の一部がアミノ基に置換された化合物）及び、ジシアンジアミド等が挙げられる。好ましくは、芳香族多価アミン及び、ジシアンジアミドであり、より好ましくは、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルエタン、１，５－ジアミノナフタレン、ｐ－フェニレンジアミン及び、ジシアンジアミドである。 Examples of the amine curing agent include aliphatic polyamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine (that is, aliphatic carbonization having 2 to 20 carbon atoms). Compounds in which part of hydrogen atoms contained in hydrogen is substituted with amino groups), p-xylenediamine, m-xylenediamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4 ′ -Diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4'-diaminodiphenyl Sulfone, bis (4-aminophen (I) Aromatic polyvalent amines such as phenylmethane (that is, some of the hydrogen atoms contained in the aromatic hydrocarbon group in the hydrocarbon having 6 to 20 carbon atoms having an aromatic hydrocarbon group are substituted with amino groups) Compound), 4,4′-diaminodicyclohexane, 1,3-bis (aminomethyl) cyclohexane and the like alicyclic polyvalent amines (that is, in hydrocarbons having 5 to 20 carbon atoms having an alicyclic hydrocarbon group) A compound in which some of the hydrogen atoms contained in the alicyclic hydrocarbon group are substituted with amino groups), dicyandiamide, and the like. Preferred are aromatic polyvalent amines and dicyandiamide, and more preferred are 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene, p-phenylenediamine and dicyandiamide. is there.
　フェノール硬化剤としては、フェノール樹脂、フェノールアラルキル樹脂（フェニレン骨格、ジフェニレン骨格等を有する）、ナフトールアラルキル樹脂及び、ポリオキシスチレン樹脂等が挙げられる。
　フェノール樹脂としては、アニリン変性レゾール樹脂及び、ジメチルエーテルレゾール樹脂等のレゾール型フェノール樹脂、フェノールノボラック樹脂、クレゾールノボラック樹脂、ｔｅｒｔ－ブチルフェノールノボラック樹脂、ノニルフェノールノボラック樹脂等のノボラック型フェノール樹脂及び、ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂等の特殊フェノール樹脂等が挙げられる。
　ポリオキシスチレン樹脂としては、ポリ（ｐ－オキシスチレン）等が挙げられる。 Examples of the phenol curing agent include a phenol resin, a phenol aralkyl resin (having a phenylene skeleton, a diphenylene skeleton, etc.), a naphthol aralkyl resin, a polyoxystyrene resin, and the like.
Examples of the phenol resin include aniline-modified resole resin, resol type phenol resin such as dimethyl ether resole resin, phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, novolac type phenol resin such as nonylphenol novolac resin, and dicyclopentadiene modified. Special phenol resins such as phenol resin, terpene-modified phenol resin, and triphenol methane type resin can be used.
Examples of the polyoxystyrene resin include poly (p-oxystyrene).
　酸無水物硬化剤としては、無水マレイン酸、無水フタル酸、無水ピロメリット酸、無水トリメリット酸、シス－４－シクロヘキセン－１，２－ジカルボン酸無水物及び、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物等が挙げられる。 Examples of the acid anhydride curing agent include maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, and 5- (2,5-dicarboxylic acid anhydride). Oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and the like.
　硬化触媒としては、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－ヘプタデシルイミダゾール及び、ベンジルジメチルアミン等が挙げられる。 Examples of the curing catalyst include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and benzyldimethylamine.
　かかる硬化剤の使用量は、用いる硬化剤の種類に応じて適宜選択される。
　硬化剤の使用量は、通常、化合物（１）が有するエポキシ基１モルに対する、硬化剤が有する、化合物（１）が有するエポキシ基と反応し得る官能基のモル数が、０．５～１．５モルとなるように調整され、好ましくは０．９～１．１モルとなるように調整される。 The amount of the curing agent used is appropriately selected according to the type of curing agent used.
The amount of the curing agent used is usually such that the molar number of the functional group that can react with the epoxy group of the compound (1) that the curing agent has is 0.5 to 1 with respect to 1 mol of the epoxy group of the compound (1). It is adjusted to be 5 mol, preferably 0.9 to 1.1 mol.
　本組成物は、さらにその他のエポキシ化合物を含んでいてもよい。
　その他のエポキシ化合物としては、ビスフェノールＡ型エポキシ化合物、オルソクレゾール型エポキシ化合物、ビフェノールジグリシジルエーテル、４，４’－ビス（３，４－エポキシブテン－１－イロキシ）フェニルベンゾエート、ナフタレンジグリシジルエーテル、α－メチルスチルベン－４，４’－ジグリシジルエーテル、４－｛４－（２，３－エポキシプロポキシ）フェニル｝シクロヘキシル　４－（２，３－エポキシプロポキシ）ベンゾエート、４－｛４－（２，３－エポキシプロポキシ）フェニル｝シクロヘキシル　４－（２，３－エポキシプロポキシ）－２－メチルベンゾエート、４－｛４－（２，３－エポキシプロポキシ）フェニル｝シクロヘキシル　４－（２，３－エポキシプロポキシ）－３－メチルベンゾエート、４－｛４－（２，３－エポキシプロポキシ）フェニル｝シクロヘキシル　４－（２，３－エポキシプロポキシ）－３－エチルベンゾエート、４－｛４－（２，３－エポキシプロポキシ）フェニル｝シクロヘキシル　４－（２，３－エポキシプロポキシ）－２－イソプロピルベンゾエート及び、４－｛４－（２，３－エポキシプロポキシ）フェニル｝シクロヘキシル　４－（２，３－エポキシプロポキシ）－３，５－ジメチルベンゾエート等が挙げられる。組成物を硬化して得られる硬化物の熱伝導性の観点から、本組成物は４－｛４－（２，３－エポキシプロポキシ）フェニル｝シクロヘキシル　４－（２，３－エポキシプロポキシ）ベンゾエートを含むと好ましい。 The composition may further contain other epoxy compounds.
Other epoxy compounds include bisphenol A type epoxy compounds, orthocresol type epoxy compounds, biphenol diglycidyl ether, 4,4′-bis (3,4-epoxybuten-1-yloxy) phenyl benzoate, naphthalene diglycidyl ether, α-methylstilbene-4,4′-diglycidyl ether, 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) benzoate, 4- {4- (2, 3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) -2-methylbenzoate, 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) -3-methylbenzoate, 4- {4- ( 2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) -3-ethylbenzoate, 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxy And propoxy) -2-isopropylbenzoate and 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) -3,5-dimethylbenzoate. From the viewpoint of thermal conductivity of a cured product obtained by curing the composition, the present composition contains 4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) benzoate. It is preferable to include.
　本組成物における、化合物（１）１００質量部に対する、その他のエポキシ化合物の含有量は、好ましくは５～１９００質量部であり、より好ましくは２０～９００質量部であり、さらに好ましくは２０～４００質量部である。その他のエポキシ化合物の含有量が５～１９００質量部であると、低い温度でプレプリグを製造することができる傾向があり、また、得られる硬化物の熱伝導性が高い傾向がある。 In the present composition, the content of the other epoxy compound with respect to 100 parts by mass of the compound (1) is preferably 5 to 1900 parts by mass, more preferably 20 to 900 parts by mass, and further preferably 20 to 400 parts by mass. Part by mass. When the content of the other epoxy compound is 5 to 1900 parts by mass, the prepreg tends to be produced at a low temperature, and the obtained cured product tends to have high thermal conductivity.
　本組成物がその他のエポキシ化合物を含む場合、本組成物に含まれる硬化剤の使用量は、通常、化合物（１）及びその他のエポキシ化合物が有するエポキシ基の合計１モルに対する、硬化剤が有する、該エポキシ基と反応し得る官能基のモル数が、０．５～１．５モルとなるように調整され、好ましくは０．９～１．１モルとなるように調整される。 When this composition contains another epoxy compound, the usage-amount of the hardening | curing agent contained in this composition has a hardening | curing agent with respect to the sum total of 1 mol of the epoxy group which a compound (1) and another epoxy compound have normally. The number of moles of the functional group capable of reacting with the epoxy group is adjusted to 0.5 to 1.5 mol, preferably 0.9 to 1.1 mol.
　本組成物は好ましくは、アルミナを含む。アルミナを含む本組成物の硬化物は、熱伝導性がより優れる傾向がある。本組成物がアルミナを含む場合、本組成物は溶媒も含むのが好ましい。
　本組成物におけるアルミナの含有量は、本組成物が含む有効成分１００質量部に対して、通常７５～９５質量部であり、好ましくは８３～９３質量部である。アルミナの含有量が７５質量部以上であると、得られる硬化物の熱伝導性がより向上し、９５質量部以下であると、本組成物の成形が容易となるため好ましい。ここで、本組成物が含む有効成分とは、本組成物が含む溶媒以外の成分のことである。 The composition preferably comprises alumina. The cured product of the present composition containing alumina tends to have better thermal conductivity. Where the composition includes alumina, the composition preferably also includes a solvent.
The content of alumina in the present composition is usually 75 to 95 parts by mass, preferably 83 to 93 parts by mass with respect to 100 parts by mass of the active ingredient contained in the present composition. When the alumina content is 75 parts by mass or more, the thermal conductivity of the resulting cured product is further improved, and when it is 95 parts by mass or less, the composition is preferably molded. Here, the active ingredient which this composition contains is components other than the solvent which this composition contains.
　アルミナは、好ましくは粒子状である。粒子状のアルミナは、好ましくは、２μｍ以上１００μｍ以下のＤ５０を有するアルミナ粒子Ａと、１μｍ以上１０μｍ以下のＤ５０を有するアルミナ粒子Ｂと、０．０１μｍ以上５μｍ以下のＤ５０を有するアルミナ粒子Ｃとを含む。本明細書におけるＤ５０とは、重量累積粒度分布の微粒子側からの累積体積５０％の粒子径のことであり、かかる粒子径は、レーザー回折法によって測定することができる。
　アルミナの体積を１００体積％としたとき、アルミナに含まれる、アルミナ粒子Ａの含有量は好ましくは５０～９０体積％であり、アルミナ粒子Ｂの含有量は好ましくは５～４０体積％であり、アルミナ粒子Ｃの含有量は好ましくは１～３０体積％である。アルミナ粒子Ａの含有量はより好ましくは６０～９０体積％であり、アルミナ粒子Ｂの含有量はより好ましくは１０～３０体積％であり、アルミナ粒子Ｃの含有量はより好ましくは５～２０体積％である。
　このようなアルミナは、市販されている種々の平均粒子径を有するアルミナ粒子を、適宜混合することにより調製することができる。 The alumina is preferably particulate. The particulate alumina preferably comprises alumina particles A having a D50 of 2 μm or more and 100 μm or less, alumina particles B having a D50 of 1 μm or more and 10 μm or less, and alumina particles C having a D50 of 0.01 μm or more and 5 μm or less. Including. In the present specification, D50 is a particle diameter of 50% cumulative volume from the fine particle side of the weight cumulative particle size distribution, and the particle diameter can be measured by a laser diffraction method.
When the volume of alumina is 100% by volume, the content of alumina particles A contained in alumina is preferably 50 to 90% by volume, and the content of alumina particles B is preferably 5 to 40% by volume, The content of alumina particles C is preferably 1 to 30% by volume. The content of alumina particles A is more preferably 60 to 90% by volume, the content of alumina particles B is more preferably 10 to 30% by volume, and the content of alumina particles C is more preferably 5 to 20% by volume. %.
Such alumina can be prepared by appropriately mixing commercially available alumina particles having various average particle sizes.
　本組成物を硬化して得られる硬化物に含まれるアルミナの含有割合は、好ましくは５０～８０体積％であり、より好ましくは６０～７４体積％である。 The content ratio of alumina contained in the cured product obtained by curing the present composition is preferably 50 to 80% by volume, more preferably 60 to 74% by volume.
　本組成物は、さらに、各種添加剤を含んでもよい。
　添加剤としては、トリフェニルホスフィン、１，８－アザビシクロ［５．４．０］－７－ウンデセン及び、２－フェニルイミダゾール等の硬化促進剤；γ－グリシドキシプロピルトリメトキシシラン等のカップリング剤；カーボンブラック等の着色剤；シリコーンオイル及び、シリコーンゴム等の低応力成分；天然ワックス、合成ワックス、高級脂肪酸、高級脂肪酸の金属塩及び、パラフィン等の離型剤；酸化防止剤；溶融破砕シリカ粉末、溶融球状シリカ粉末、結晶シリカ粉末及び、二次凝集シリカ粉末等のシリカ又はその粉末；チタンホワイト；水酸化アルミニウム；タルク；クレイ；マイカ並びに、ガラス繊維等が挙げられる。
　本組成物における各種添加剤の含有量は、融点等の所望の性能の低下させない程度で適宜調整される。 The present composition may further contain various additives.
Additives include curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, and 2-phenylimidazole; couplings such as γ-glycidoxypropyltrimethoxysilane Agents; Colorants such as carbon black; Low stress components such as silicone oil and silicone rubber; Mold release agents such as natural wax, synthetic wax, higher fatty acid, metal salt of higher fatty acid and paraffin; Antioxidant; Examples thereof include silica such as silica powder, fused spherical silica powder, crystalline silica powder and secondary agglomerated silica powder or powder thereof; titanium white; aluminum hydroxide; talc; clay; mica and glass fiber.
Content of the various additives in this composition is suitably adjusted in the grade which does not reduce desired performance, such as melting | fusing point.
　本組成物を硬化して得られる硬化物（以下、本硬化物ということがある。）の製造方法としては、本組成物をそのまま所定温度まで加熱して硬化させる方法；本組成物を加熱溶融して金型等に注ぎ、該金型をさらに加熱して成形する方法；本組成物を溶融させ、得られる溶融物を予め加熱された金型に注入し硬化する方法；本組成物を部分硬化させ、得られる部分硬化物を粉砕し、得られた粉末を金型に充填し、該充填粉末を溶融成形する方法及び；本組成物を必要に応じて溶媒に溶解し、攪拌しながら部分硬化させ、得られた溶液をキャストした後、溶媒を通風乾燥等で乾燥除去し、必要に応じてプレス機等で圧力をかけながら所定時間加熱する方法等が挙げられる。本組成物がアルミナを含む場合は、通常、本組成物をそのまま所定温度まで加熱して硬化させる方法；本組成物を加熱溶融して金型等に注ぎ、該金型をさらに加熱して成形する方法；本組成物を溶融させ、得られる溶融物を予め加熱された金型に注入し硬化する方法又は；本組成物を部分硬化させ、得られる部分硬化物を粉砕し、得られた粉末を金型に充填し、該充填粉末を溶融成形する方法によって硬化物は製造される。 A method for producing a cured product obtained by curing the composition (hereinafter sometimes referred to as a cured product) is a method of curing the composition by heating it to a predetermined temperature as it is; melting and heating the composition The composition is then poured into a mold and the mold is further heated to form; the composition is melted; the resulting melt is poured into a preheated mold and cured; the composition is partially A method of curing, pulverizing the partially cured product obtained, filling the obtained powder into a mold, and melt-molding the filled powder; and dissolving the composition in a solvent as necessary and stirring the part Examples include a method of curing and casting the obtained solution, followed by drying and removing the solvent by ventilation drying or the like, and heating for a predetermined time while applying pressure with a press machine or the like as necessary. When the composition contains alumina, usually, the composition is heated to a predetermined temperature as it is to cure; the composition is heated and melted and poured into a mold, and the mold is further heated to form. A method of melting the composition and injecting the resulting melt into a preheated mold and curing; or a method of partially curing the composition and pulverizing the resulting partially cured product. A cured product is produced by a method of filling a mold and melt-molding the filled powder.
　次に、本組成物を用いたプリプレグの製造方法について説明する。
　溶媒を含む本組成物をそのまま、又は、さらに溶媒で希釈し、基材に塗布もしくは含浸させた後、得られた基材を加熱して、該基材中の化合物（１）を半硬化させることによりプリプレグを得ことができる。得られたプリプレグを、複数個、積層してプレス等により加圧及び加熱することにより積層板を得ることもできる。
　プリプレグの製造に用いられる基材としては、ガラス繊維、炭素繊維等の無機質繊維の織布若しくは不織布、ポリエステル等の有機質繊維の織布若しくは不織布等が挙げられる。
　前記加熱温度は、好ましくは７０～１３０℃であり、より好ましくは７０～１２５℃であり、さらに好ましくは７０～１２０℃である。本組成物は７０℃～１３０℃程度の温度で硬化が進むためプリプレグの製造が容易であり、生産性が高くなるため好ましい。 Next, the manufacturing method of the prepreg using this composition is demonstrated.
The present composition containing a solvent is used as it is, or further diluted with a solvent and applied or impregnated on a substrate, and then the obtained substrate is heated to semi-cur the compound (1) in the substrate. Thus, a prepreg can be obtained. A laminated board can also be obtained by laminating a plurality of the obtained prepregs and pressing and heating them with a press or the like.
Examples of the base material used for producing the prepreg include woven or nonwoven fabrics of inorganic fibers such as glass fibers and carbon fibers, and woven or nonwoven fabrics of organic fibers such as polyester.
The heating temperature is preferably 70 to 130 ° C, more preferably 70 to 125 ° C, and further preferably 70 to 120 ° C. This composition is preferable because curing proceeds at a temperature of about 70 ° C. to 130 ° C., so that the prepreg can be easily produced and the productivity becomes high.
　以下、実施例により本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
＜ＬＣ分析条件＞
液体クロマトグラフィーによる測定は、島津製作所製高速液体クロマトグラフＰｒｏｍｉｎｅｎｃｅ低圧グラジエントシステム（カラム：化学物質評価研究機構製Ｌ－ｃｏｌｕｍｎ　ＯＤＳ、カラム温度：４０℃、検出器：ＵＶ２５４ｎｍ、移動相：アセトニトリル／水、流速：１ｍＬ／ｍｉｎ）を用いて行った。 <LC analysis conditions>
The measurement by liquid chromatography was performed by Shimadzu High Performance Liquid Chromatograph Prominence Low Pressure Gradient System (column: L-column ODS manufactured by Chemical Substance Evaluation Research Organization, column temperature: 40 ° C., detector: UV254 nm, mobile phase: acetonitrile / water, Flow rate: 1 mL / min).
［実施例１：ジヒドロキシ化合物（２）の製造例１］
　式（２－１）で表わされる４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェニル）プロパノエート（以下、ジヒドロキシ化合物（２－１）と記すことがある。）の製造例。
Figure JPOXMLDOC01-appb-C000018
 　精留塔を備えた反応容器内にて、３－（４－ヒドロキシフェニル）プロピオン酸メチル１３９ｍｍｏｌ、４－（４－ヒドロキシシクロヘキシル）フェノール１３９ｍｍｏｌ、ジブチルスズオキシド２．８ｍｍｏｌ及び４－クロロトルエン１２５ｇを混合した。得られた混合物を加熱還流しながら１０時間攪拌した後、室温まで冷却した。この際、反応の進行に伴って生成したアルコールは精留塔を用いて反応容器内から除去した。その後、室温まで冷却された混合物から析出した固体を濾過により分離することにより、粗生成物を得た。
　得られた粗生成物をメタノール３７ｇで洗浄した後、６０℃で減圧乾燥し、ジヒドロキシ化合物（２－１）を含む白色結晶３５．７ｇを得た。
　得られた結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラムの面積百分率を算出したところ、９３．３％であった。当該結晶中のジヒドロキシ化合物（２－１）の含有量を９３．３質量％と仮定すると、３－（４－ヒドロキシフェニル）プロピオン酸メチルを基準とするジヒドロキシ化合物（２－１）の収率は、７４％であった。 [Example 1: Production Example 1 of dihydroxy compound (2)]
Production example of 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenyl) propanoate represented by the formula (2-1) (hereinafter sometimes referred to as dihydroxy compound (2-1)).
Figure JPOXMLDOC01-appb-C000018
 In a reaction vessel equipped with a rectifying column, 139 mmol of methyl 3- (4-hydroxyphenyl) propionate, 139 mmol of 4- (4-hydroxycyclohexyl) phenol, 2.8 mmol of dibutyltin oxide and 125 g of 4-chlorotoluene were mixed. . The resulting mixture was stirred for 10 hours while being heated to reflux, and then cooled to room temperature. At this time, the alcohol produced as the reaction progressed was removed from the reaction vessel using a rectification column. Then, the crude product was obtained by isolate | separating the solid which precipitated from the mixture cooled to room temperature by filtration.
The obtained crude product was washed with 37 g of methanol and then dried under reduced pressure at 60 ° C. to obtain 35.7 g of white crystals containing the dihydroxy compound (2-1).
The obtained crystals were analyzed by liquid chromatography, and the area percentage of the obtained chromatogram was calculated to be 93.3%. Assuming that the content of the dihydroxy compound (2-1) in the crystal is 93.3% by mass, the yield of the dihydroxy compound (2-1) based on methyl 3- (4-hydroxyphenyl) propionate is 74%.
　得られたジヒドロキシ化合物（２－１）のスペクトルデータを以下に示す。
１Ｈ－ＮＭＲ（δ：ｐｐｍ，ＤＭＳＯ－ｄ６）　１．４４（ｍ，４Ｈ），１．７６（ｍ，２Ｈ），１．９２（ｍ，２Ｈ），２．３９（１Ｈ），２．５２（２Ｈ），２．７３（２Ｈ），４．６６（ｃ，１Ｈ），６．６６（ｃ，４Ｈ），７．０１（ｃ，４Ｈ），９．１７（ｂｒ，２Ｈ）． The spectral data of the obtained dihydroxy compound (2-1) is shown below.
1 H-NMR (δ: ppm, DMSO-d 6 ) 1.44 (m, 4H), 1.76 (m, 2H), 1.92 (m, 2H), 2.39 (1H), 2. 52 (2H), 2.73 (2H), 4.66 (c, 1H), 6.66 (c, 4H), 7.01 (c, 4H), 9.17 (br, 2H).
［実施例２：ジヒドロキシ化合物（２）の製造例２］
　式（２－２）で表わされる４－（４－ヒドロキシフェニル）シクロヘキシル　３－（３－メチル－４－ヒドロキシフェニル）プロパノエート（以下、ジヒドロキシ化合物（２－２）と記すことがある）の製造例。
Figure JPOXMLDOC01-appb-C000019
 　精留塔を取り付けた反応容器内にて、３－（３－メチル－４－ヒドロキシフェニル）プロピオン酸メチル８６ｍｍｏｌ、４－（４－ヒドロキシシクロヘキシル）フェノール８６ｍｍｏｌ、ジブチルスズオキシド１．７ｍｍｏｌ及び４－クロロトルエン８４ｇを混合した。得られた混合物を加熱還流しながら１０時間攪拌した後、室温まで冷却した。この際、反応の進行に伴って生成したアルコールは精留塔を用いて反応容器内から除去した。その後、室温まで冷却された混合物から析出した固体を濾過により分離することにより、粗生成物を得た。
　得られた粗生成物をｎ－ヘプタン３０ｇで洗浄した後、６０℃で減圧乾燥し、ジヒドロキシ化合物（２－２）を含む白色結晶２３．９ｇを得た。
　得られた結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラムの面積百分率を算出したところ、７８．６％であった。当該結晶中のジヒドロキシ化合物（２－２）の含有量を７８．６質量％と仮定すると、３－（３－メチル－４－ヒドロキシフェニル）プロピオン酸メチルを基準とするジヒドロキシ化合物（２－２）の収率は、６１％であった。 [Example 2: Production Example 2 of dihydroxy compound (2)]
Production example of 4- (4-hydroxyphenyl) cyclohexyl 3- (3-methyl-4-hydroxyphenyl) propanoate represented by formula (2-2) (hereinafter sometimes referred to as dihydroxy compound (2-2)) .
Figure JPOXMLDOC01-appb-C000019
 In a reaction vessel equipped with a rectifying column, 86 mmol of methyl 3- (3-methyl-4-hydroxyphenyl) propionate, 86 mmol of 4- (4-hydroxycyclohexyl) phenol, 1.7 mmol of dibutyltin oxide and 4-chlorotoluene 84 g was mixed. The resulting mixture was stirred for 10 hours while being heated to reflux, and then cooled to room temperature. At this time, the alcohol produced as the reaction progressed was removed from the reaction vessel using a rectification column. Then, the crude product was obtained by isolate | separating the solid which precipitated from the mixture cooled to room temperature by filtration.
The obtained crude product was washed with 30 g of n-heptane and then dried under reduced pressure at 60 ° C. to obtain 23.9 g of white crystals containing the dihydroxy compound (2-2).
The obtained crystals were analyzed by liquid chromatography, and the area percentage of the obtained chromatogram was calculated to be 78.6%. Assuming that the content of the dihydroxy compound (2-2) in the crystal is 78.6% by mass, the dihydroxy compound (2-2) based on methyl 3- (3-methyl-4-hydroxyphenyl) propionate The yield of was 61%.
　得られたジヒドロキシ化合物（２－２）のスペクトルデータを以下に示す。
１Ｈ－ＮＭＲ（δ：ｐｐｍ，ＤＭＳＯ－ｄ６）　１．４５（ｍ，４Ｈ），１．７７（ｍ，２Ｈ），１．９３（ｍ，２Ｈ），２．０６（ｓ，３Ｈ），２．３９（ｃ，１Ｈ），２．５３（２Ｈ），２．７０（ｃ，２Ｈ），４．６６（ｃ，１Ｈ），６．６６（ｃ，３Ｈ），６．８１（ｃ，１Ｈ），６．８８（１Ｈ），７．０１（ｃ，２Ｈ），９．１１（ｂｒ，２Ｈ）． The spectral data of the obtained dihydroxy compound (2-2) is shown below.
1 H-NMR (δ: ppm, DMSO-d 6 ) 1.45 (m, 4H), 1.77 (m, 2H), 1.93 (m, 2H), 2.06 (s, 3H), 2.39 (c, 1H), 2.53 (2H), 2.70 (c, 2H), 4.66 (c, 1H), 6.66 (c, 3H), 6.81 (c, 1H) ), 6.88 (1H), 7.01 (c, 2H), 9.11 (br, 2H).
［実施例３：ジヒドロキシ化合物（２）の製造例３］
　式（２－３）で表わされる４－（４－ヒドロキシフェニル）シクロヘキシル　３－（４－ヒドロキシフェノキシ）　アセテート（以下、ジヒドロキシ化合物（２－３）と記すことがある）の製造例。
Figure JPOXMLDOC01-appb-C000020
 　精留塔を取り付けた反応容器内にて、３－（４－ヒドロキシフェノキシ）酢酸メチル１２１ｍｍｏｌ、４－（４－ヒドロキシシクロヘキシル）フェノール１２１ｍｍｏｌ、ジブチルスズオキシド２．０ｍｍｏｌ及び４－クロロトルエン１１０ｇを混合した。得られた混合物を加熱還流しながら１０時間攪拌した後、室温まで冷却した。この際、反応の進行に伴って生成したアルコールは精留塔を用いて反応容器内から除去した。その後、室温まで冷却された混合物から析出した固体を濾過により分離することにより、粗生成物を得た。
　得られた粗生成物をｎ－ヘプタン２２ｇおよび２－プロパノール２２ｇで洗浄した後、６０℃で減圧乾燥し、ジヒドロキシ化合物（２－３）を含む白色結晶３７．５ｇを得た。
　得られた結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラムの面積百分率を算出したところ、９６．０％であった。当該結晶中のジヒドロキシ化合物（２－３）の含有量を９６．０重量％と仮定すると、３－（４－ヒドロキシフェノキシ）酢酸メチルを基準とするジヒドロキシ化合物（２－３）の収率は、８７％であった。 [Example 3: Production Example 3 of dihydroxy compound (2)]
Production example of 4- (4-hydroxyphenyl) cyclohexyl 3- (4-hydroxyphenoxy) acetate represented by the formula (2-3) (hereinafter sometimes referred to as dihydroxy compound (2-3)).
Figure JPOXMLDOC01-appb-C000020
 In a reaction vessel equipped with a rectifying column, 121 mmol of methyl 3- (4-hydroxyphenoxy) acetate, 121 mmol of 4- (4-hydroxycyclohexyl) phenol, 2.0 mmol of dibutyltin oxide and 110 g of 4-chlorotoluene were mixed. The resulting mixture was stirred for 10 hours while being heated to reflux, and then cooled to room temperature. At this time, the alcohol produced as the reaction progressed was removed from the reaction vessel using a rectification column. Then, the crude product was obtained by isolate | separating the solid which precipitated from the mixture cooled to room temperature by filtration.
The obtained crude product was washed with 22 g of n-heptane and 22 g of 2-propanol, and then dried under reduced pressure at 60 ° C. to obtain 37.5 g of white crystals containing the dihydroxy compound (2-3).
The obtained crystals were analyzed by liquid chromatography, and the area percentage of the obtained chromatogram was calculated to be 96.0%. Assuming that the content of the dihydroxy compound (2-3) in the crystal is 96.0% by weight, the yield of the dihydroxy compound (2-3) based on methyl 3- (4-hydroxyphenoxy) acetate is 87%.
　得られたジヒドロキシ化合物（２－３）のスペクトルデータを以下に示す。
１Ｈ－ＮＭＲ（δ：ｐｐｍ，ＤＭＳＯ－ｄ６）　１．４８（ｍ，４Ｈ），１．７９（ｍ，２Ｈ），１．９９（ｍ，２Ｈ），２．４１（ｃ，１Ｈ），４．６３（ｓ，２Ｈ），４．７８（ｃ，１Ｈ），６．７１（６Ｈ），７．０２（ｃ，２Ｈ），８．９９（ｓ，１Ｈ），９．１３（ｓ，１Ｈ）． The spectral data of the obtained dihydroxy compound (2-3) is shown below.
1 H-NMR (δ: ppm, DMSO-d 6 ) 1.48 (m, 4H), 1.79 (m, 2H), 1.99 (m, 2H), 2.41 (c, 1H), 4.63 (s, 2H), 4.78 (c, 1H), 6.71 (6H), 7.02 (c, 2H), 8.99 (s, 1H), 9.13 (s, 1H) ).
［実施例４：ジエポキシ化合物（１）の製造例１］
　式（１－１）で表わされる４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェニル］プロパノエート（以下、ジエポキシ化合物（１－１）と記すことがある。）の製造例。
Figure JPOXMLDOC01-appb-C000021
 　ジヒドロキシ化合物（２－１）４４ｍｍｏｌ、テトラブチルアンモニウムブロミド８．８ｍｍｏｌ）及び、エピクロロヒドリン１３２１ｍｍｏｌを、７０℃で１２時間攪拌混合した後、２５℃まで冷却した。得られた反応液に、モノクロロベンゼン１５０ｇ及び、７質量％の水酸化ナトリウム水溶液７８ｇを加え、室温で２時間攪拌した。得られた混合物に、水を加えて分液洗浄した後、濃縮して粗生成物を得た。得られた粗生成物を、２－プロパノールを用いて再結晶精製した後、乾燥し、白色結晶１７．３ｇを得た。
　該白色結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラムの面積百分率を算出したところ、９５．７％であった。該白色結晶中のジエポキシ化合物（１－１）の含有量を９５．７質量％と仮定すると、ジヒドロキシ化合物（２－１）を基準とするジエポキシ化合物（１－１）の収率は８４％であった。該白色結晶の融点は９６℃であった。 [Example 4: Production Example 1 of diepoxy compound (1)]
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenyl] propanoate represented by formula (1-1) (hereinafter referred to as diepoxy compound (1-1) ))).
Figure JPOXMLDOC01-appb-C000021
 Dihydroxy compound (2-1) 44 mmol, tetrabutylammonium bromide 8.8 mmol) and epichlorohydrin 1321 mmol were stirred and mixed at 70 ° C. for 12 hours, and then cooled to 25 ° C. To the obtained reaction liquid, 150 g of monochlorobenzene and 78 g of a 7% by mass aqueous sodium hydroxide solution were added and stirred at room temperature for 2 hours. Water was added to the resulting mixture to separate and wash it, and then concentrated to obtain a crude product. The obtained crude product was recrystallized and purified using 2-propanol and then dried to obtain 17.3 g of white crystals.
The white crystals were analyzed by liquid chromatography, and the area percentage of the obtained chromatogram was calculated to be 95.7%. Assuming that the content of the diepoxy compound (1-1) in the white crystal is 95.7% by mass, the yield of the diepoxy compound (1-1) based on the dihydroxy compound (2-1) is 84%. there were. The melting point of the white crystals was 96 ° C.
　得られたジエポキシ化合物（１－１）のスペクトルデータを以下に示す。
１Ｈ－ＮＭＲ（δ：ｐｐｍ，ＤＭＳＯ－ｄ６）　１．４６（ｍ，４Ｈ），１．７７（ｍ，２Ｈ），１．９３（ｍ，２Ｈ），２．５２（５Ｈ），２．６９（２Ｈ），２．８０（４Ｈ），３．３１（ｃ，２Ｈ），３．７８（ｃ，２Ｈ），４．２８（ｃ，２Ｈ），４．６７（ｃ，１Ｈ），６．８７（ｃ，４Ｈ），７．１４（ｃ，４Ｈ）． The spectral data of the obtained diepoxy compound (1-1) is shown below.
1 H-NMR (δ: ppm, DMSO-d 6 ) 1.46 (m, 4H), 1.77 (m, 2H), 1.93 (m, 2H), 2.52 (5H), 2. 69 (2H), 2.80 (4H), 3.31 (c, 2H), 3.78 (c, 2H), 4.28 (c, 2H), 4.67 (c, 1H), 6. 87 (c, 4H), 7.14 (c, 4H).
［実施例５：ジエポキシ化合物（１）の製造例２］
　式（１－２）で表わされる４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［３－メチル－４－（２，３－エポキシプロポキシ）フェニル］プロパノエート（以下、ジエポキシ化合物（１－２）と記すことがある。）の製造例。
Figure JPOXMLDOC01-appb-C000022
 　ジヒドロキシ化合物（２－２）４４ｍｍｏｌ、テトラブチルアンモニウムブロミド８．５ｍｍｏｌ及び、エピクロロヒドリン１６９３ｍｍｏｌを、７０℃で１２時間攪拌混合した後、２５℃まで冷却した。得られた反応液に、モノクロロベンゼン１５０ｇ及び、７重量％の水酸化ナトリウム水溶液７５ｇを加え、室温で２時間攪拌した。得られた混合物に、水を加えて分液洗浄した後、濃縮して粗生成物を得た。得られた粗生成物を、２－プロパノールを用いて再結晶精製した後、乾燥し、白色結晶１１．９ｇを得た。
　該白色結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラムの面積百分率を算出したところ、９３．３％であった。該白色結晶中のジエポキシ化合物（１－２）の含有量を９３．３質量％と仮定すると、ジヒドロキシ化合物（２－２）を基準とするジエポキシ化合物（１－２）の収率は５６％であった。該白色固体の融点は７５℃であった。 [Example 5: Production Example 2 of diepoxy compound (1)]
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [3-methyl-4- (2,3-epoxypropoxy) phenyl] propanoate represented by the formula (1-2) (hereinafter referred to as diepoxy compound) (1-2))).
Figure JPOXMLDOC01-appb-C000022
 44 mmol of the dihydroxy compound (2-2), 8.5 mmol of tetrabutylammonium bromide and 1693 mmol of epichlorohydrin were stirred and mixed at 70 ° C. for 12 hours, and then cooled to 25 ° C. To the obtained reaction liquid, 150 g of monochlorobenzene and 75 g of a 7% by weight aqueous sodium hydroxide solution were added and stirred at room temperature for 2 hours. Water was added to the resulting mixture to separate and wash it, and then concentrated to obtain a crude product. The obtained crude product was recrystallized and purified using 2-propanol and then dried to obtain 11.9 g of white crystals.
The white crystals were analyzed by liquid chromatography, and the area percentage of the obtained chromatogram was calculated to be 93.3%. Assuming that the content of the diepoxy compound (1-2) in the white crystal is 93.3% by mass, the yield of the diepoxy compound (1-2) based on the dihydroxy compound (2-2) is 56%. there were. The melting point of the white solid was 75 ° C.
　得られたジエポキシ化合物（１－２）のスペクトルデータを以下に示す。
１Ｈ－ＮＭＲ（δ：ｐｐｍ，ＤＭＳＯ－ｄ６）　１．４７（ｍ，４Ｈ），１．７８（ｍ，２Ｈ），１．９３（ｍ，２Ｈ），２．１４（ｓ，３Ｈ），２．５１（３Ｈ），２．７３（４Ｈ），２．８３（ｃ，２Ｈ），３．１３（ｃ，２Ｈ），３．８０（ｃ，２Ｈ），４．２７（ｃ，２Ｈ），４．６７（ｃ，１Ｈ），６．８５（３Ｈ），６．９９（２Ｈ），７．１６（２Ｈ）． The spectral data of the obtained diepoxy compound (1-2) is shown below.
1 H-NMR (δ: ppm, DMSO-d 6 ) 1.47 (m, 4H), 1.78 (m, 2H), 1.93 (m, 2H), 2.14 (s, 3H), 2.51 (3H), 2.73 (4H), 2.83 (c, 2H), 3.13 (c, 2H), 3.80 (c, 2H), 4.27 (c, 2H), 4.67 (c, 1H), 6.85 (3H), 6.99 (2H), 7.16 (2H).
［実施例６：ジエポキシ化合物（１）の製造例３］
　式（１－３）で表わされる４－［４－（２，３－エポキシプロポキシ）フェニル］シクロヘキシル　３－［４－（２，３－エポキシプロポキシ）フェノキシ］アセテート（以下、ジエポキシ化合物（１－３）と記すことがある。）の製造例。
Figure JPOXMLDOC01-appb-C000023
 　ジヒドロキシ化合物（２－３）５０ｍｍｏｌ、テトラブチルアンモニウムブロミド９．９ｍｍｏｌ）、エピクロロヒドリン１４９３ｍｍｏｌを、６０℃で１０時間攪拌混合した後、２５℃まで冷却した。得られた反応液に７質量％の水酸化ナトリウム水溶液８８ｇを加え、室温で２時間攪拌した。得られた混合物に、水を加えて分液洗浄した後、濃縮して粗生成物を得た。得られた粗生成物を、２－プロパノールを用いて再結晶精製した後、乾燥し、白色結晶２０．５ｇを得た。
　該白色結晶を液体クロマトグラフィーによって分析し、得られたクロマトグラムの面積百分率を算出したところ、９４．０％であった。該結晶中のジエポキシ化合物（１－３）の含有量を９４．０重量％と仮定すると、ジヒドロキシ化合物（２－３）を基準とするジエポキシ化合物（１－３）の収率は８５％であった。該白色結晶の融点は１１２℃であった。 [Example 6: Production Example 3 of diepoxy compound (1)]
4- [4- (2,3-epoxypropoxy) phenyl] cyclohexyl 3- [4- (2,3-epoxypropoxy) phenoxy] acetate (hereinafter referred to as diepoxy compound (1-3) represented by formula (1-3) ))).
Figure JPOXMLDOC01-appb-C000023
 Dihydroxy compound (2-3) 50 mmol, tetrabutylammonium bromide 9.9 mmol) and epichlorohydrin 1493 mmol were stirred and mixed at 60 ° C. for 10 hours, and then cooled to 25 ° C. To the obtained reaction solution, 88 g of a 7% by mass aqueous sodium hydroxide solution was added and stirred at room temperature for 2 hours. Water was added to the resulting mixture to separate and wash it, and then concentrated to obtain a crude product. The obtained crude product was recrystallized and purified using 2-propanol and then dried to obtain 20.5 g of white crystals.
The white crystals were analyzed by liquid chromatography, and the area percentage of the obtained chromatogram was calculated to be 94.0%. Assuming that the content of diepoxy compound (1-3) in the crystal is 94.0% by weight, the yield of diepoxy compound (1-3) based on dihydroxy compound (2-3) was 85%. It was. The melting point of the white crystals was 112 ° C.
　得られたジエポキシ化合物（１－３）のスペクトルデータを以下に示す。
１Ｈ－ＮＭＲ（δ：ｐｐｍ，ＤＭＳＯ－ｄ６）　１．５２（ｍ，４Ｈ），１．８１（ｍ，２Ｈ），２．００（ｍ，２Ｈ），２．５０（３Ｈ），２．６９（２Ｈ），２．８３（２Ｈ），３．３１（ｍ，２Ｈ），３．７８（ｍ，２Ｈ），４．２７（ｃ，２Ｈ），４．７０（ｃ，２Ｈ），４．８０（ｃ，１Ｈ），６．８７（６Ｈ），７．１７（２Ｈ）． The spectral data of the obtained diepoxy compound (1-3) is shown below.
1 H-NMR (δ: ppm, DMSO-d 6 ) 1.52 (m, 4H), 1.81 (m, 2H), 2.00 (m, 2H), 2.50 (3H), 2. 69 (2H), 2.83 (2H), 3.31 (m, 2H), 3.78 (m, 2H), 4.27 (c, 2H), 4.70 (c, 2H), 4. 80 (c, 1H), 6.87 (6H), 7.17 (2H).
［実施例７：組成物及びその硬化物の製造例１］
　実施例４で得られたジエポキシ化合物（１－１）含む白色結晶１００質量部と、１，５－ジアミノナフタレン（和光純薬工業株式会社製）１６質量部と、アルミナ粉末１０６８質量部（住友化学株式会社製のα－アルミナ粉末３種を混合して調整した。混合比は次の通りである。アルミナ粉末Ａ１（Ｄ５０：１８μ）／アルミナ粉末Ｂ１（Ｄ５０：３μｍ）／アルミナ粉末Ｃ１（Ｄ５０：０．４μｍ）＝＜質量比＞７４９／１４９／１２８、＜体積比＞７４／１４／１２）と、メチルイソブチルケトン５３０質量部と、Ｎ，Ｎ－ジメチルホルムアミド６０質量部と、を混合し組成物（１）を調製した。ポリエチレンテレフタレート（ＰＥＴ）フィルム基材上に、アプリケータを用いて、組成物（１）を厚さが３５０μｍになるよう塗布した。組成物（１）が塗布されたＰＥＴフィルムを室温で１時間乾燥し、さらに１２０℃で１０分間加熱乾燥し、半硬化させ、溶媒を留去した後、ＰＥＴフィルムを剥がし、プリプレグシートを得た。
　得られたプリプレグシートを厚さ４０μｍのアルミ箔で挟み、真空プレス成形（プレス温度：１３０℃、真空度：１ｋＰａ、プレス圧：６ＭＰａ、処理時間：２０分）を行い、その後さらに、４０分かけてプレス温度を１８０℃まで昇温した。プレス成形後、アルミ箔を剥がし、厚さ３２０μｍのシート状の硬化物を得た。
　ＮＥＴＺＳＣＨ製キセノンフラッシュアナライザー　ｎａｎｏｆｌａｓｈ　ＬＦＡ４４７型を用いて、得られた該硬化物の熱伝導率を測定したところ、７．２Ｗ／（ｍ・Ｋ）であった。
　ジエポキシ化合物（１－１）と１，５－ジアミノナフタレンとを含み、アルミナ粉末を含まない組成物を硬化させることにより得られる硬化物の密度を１．２ｇ／ｃｍ３、アルミナ粉末の密度を３．９７ｇ／ｃｍ３として、得られた硬化物中のアルミナ粉末の含有割合を算出したところ、該硬化物中のアルミナ粉末の含有割合は、７４体積％であった。 [Example 7: Production Example 1 of composition and cured product thereof]
100 parts by mass of white crystals containing the diepoxy compound (1-1) obtained in Example 4, 16 parts by mass of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.), and 1068 parts by mass of alumina powder (Sumitomo Chemical) The mixture was adjusted by mixing three types of α-alumina powder manufactured by Co., Ltd. The mixing ratio was as follows: Alumina powder A1 (D50: 18 μ) / Alumina powder B1 (D50: 3 μm) / Alumina powder C1 (D50: 0.4 μm) = <mass ratio> 749/149/128, <volume ratio> 74/14/12), 530 parts by mass of methyl isobutyl ketone, and 60 parts by mass of N, N-dimethylformamide. A product (1) was prepared. The composition (1) was applied on a polyethylene terephthalate (PET) film substrate using an applicator so that the thickness was 350 μm. The PET film coated with the composition (1) was dried at room temperature for 1 hour, further heated and dried at 120 ° C. for 10 minutes, semi-cured, and after the solvent was distilled off, the PET film was peeled off to obtain a prepreg sheet. .
The obtained prepreg sheet was sandwiched between aluminum foils having a thickness of 40 μm, and vacuum press molding (press temperature: 130 ° C., degree of vacuum: 1 kPa, press pressure: 6 MPa, treatment time: 20 minutes) was performed, and then over 40 minutes. The press temperature was raised to 180 ° C. After the press molding, the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 320 μm.
When the thermal conductivity of the obtained cured product was measured using a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH, it was 7.2 W / (m · K).
The density of the cured product obtained by curing the composition containing the diepoxy compound (1-1) and 1,5-diaminonaphthalene and not the alumina powder is 1.2 g / cm 3 , and the density of the alumina powder is 3 The content ratio of the alumina powder in the obtained cured product was calculated as .97 g / cm 3 , and the content ratio of the alumina powder in the cured product was 74% by volume.
［比較例１］
　下記式（９）および下記式（１０）で示される化合物が１：１の割合で含まれるビフェニル型エポキシモノマーＹＬ６１２１Ｈ（ジャパンエポキシレジン製）１００質量部と、１，５－ジアミノナフタレン（和光純薬工業株式会社製）２４質量部と、アルミナ粉末１１４６質量部（住友化学株式会社製のα－アルミナ粉末３種を混合して調整した。混合比は次の通りである。アルミナ粉末Ａ１（Ｄ５０：１８μ）／アルミナ粉末Ｂ１（Ｄ５０：３μｍ）／アルミナ粉末Ｃ１（Ｄ５０：０．４μｍ）＝＜質量比＞８４８／１６０／１３２、＜体積比＞７４／１４／１２）と、メチルイソブチルケトン５３０質量部と、Ｎ，Ｎ－ジメチルホルムアミド６０質量部と、を混合し組成物（２）を調製した。ポリエチレンテレフタレート（ＰＥＴ）フィルム上に、アプリケータを用いて、組成物（２）を厚さが３５０μｍになるよう塗布した。組成物（２）が塗布されたＰＥＴフィルムを室温で１時間乾燥し、さらに１２０℃で１０分間加熱乾燥したが、上記エポキシモノマーが十分に融解せず、半硬化物が得られなかった。
Figure JPOXMLDOC01-appb-C000024
 [Comparative Example 1]
100 parts by mass of a biphenyl type epoxy monomer YL6121H (manufactured by Japan Epoxy Resin) containing a compound represented by the following formula (9) and the following formula (10) in a ratio of 1: 1, and 1,5-diaminonaphthalene (Wako Pure Chemical Industries, Ltd.) 24 parts by mass manufactured by Kogyo Co., Ltd. and 1146 parts by mass of alumina powder (3 types of α-alumina powder manufactured by Sumitomo Chemical Co., Ltd.) were mixed and mixed at the following ratio: Alumina powder A1 (D50: 18 μ) / alumina powder B1 (D50: 3 μm) / alumina powder C1 (D50: 0.4 μm) = <mass ratio> 848/160/132, <volume ratio> 74/14/12), and methyl isobutyl ketone 530 mass Part and 60 parts by mass of N, N-dimethylformamide were mixed to prepare composition (2). The composition (2) was applied on a polyethylene terephthalate (PET) film so as to have a thickness of 350 μm using an applicator. The PET film coated with the composition (2) was dried at room temperature for 1 hour and further heated and dried at 120 ° C. for 10 minutes. However, the epoxy monomer was not sufficiently melted and a semi-cured product was not obtained.
Figure JPOXMLDOC01-appb-C000024
［比較例２］
　ポリエチレンテレフタレート（ＰＥＴ）フィルム基材上に、アプリケータを用いて、組成物（２）を厚さが３５０μｍになるよう塗布した。組成物（２）が塗布されたＰＥＴフィルムを室温で１時間乾燥し、さらに１４０℃で１０分間加熱乾燥し、半硬化させ、溶媒を留去した後、ＰＥＴフィルムを剥がし、プリプレグシートを得た。
　得られたプリプレグシートを厚さ４０μｍのアルミ箔で挟み、真空プレス成形（プレス温度：１４０℃、真空度：１ｋＰａ、プレス圧：６ＭＰａ、処理時間：２０分）を行い、その後さらに、４０分かけてプレス温度を１８０℃まで昇温した。プレス成形後、アルミ箔を剥がし、厚さ３９８μｍのシート状の硬化物を得た。
　ＮＥＴＺＳＣＨ製キセノンフラッシュアナライザー　ｎａｎｏｆｌａｓｈ　ＬＦＡ４４７型を用いて、得られた硬化物の熱伝導率を測定したところ、６．９Ｗ／（ｍ・Ｋ）であった。 [Comparative Example 2]
The composition (2) was applied onto a polyethylene terephthalate (PET) film substrate using an applicator so that the thickness was 350 μm. The PET film coated with the composition (2) was dried at room temperature for 1 hour, further heated and dried at 140 ° C. for 10 minutes, semi-cured, and after the solvent was distilled off, the PET film was peeled off to obtain a prepreg sheet. .
The obtained prepreg sheet was sandwiched between aluminum foils having a thickness of 40 μm, and vacuum press molding (press temperature: 140 ° C., vacuum degree: 1 kPa, press pressure: 6 MPa, treatment time: 20 minutes) was performed, and then, for 40 minutes. The press temperature was raised to 180 ° C. After press molding, the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 398 μm.
When the thermal conductivity of the obtained cured product was measured using a xenon flash analyzer nanoflash LFA447 manufactured by NETZSCH, it was 6.9 W / (m · K).
　本発明のジエポキシ化合物は融点が低いため、より低い温度でプリプレグを製造することができた。さらに、本発明のジエポキシ化合物と硬化剤とを含む組成物の硬化物は、熱伝導性に優れていた。 Since the diepoxy compound of the present invention has a low melting point, a prepreg could be produced at a lower temperature. Furthermore, the hardened | cured material of the composition containing the diepoxy compound of this invention and a hardening | curing agent was excellent in thermal conductivity.
　本発明のジエポキシ化合物は融点が低く、また、該ジエポキシ化合物から得られる硬化物は熱伝導性に優れるため有用である。 The diepoxy compound of the present invention has a low melting point, and a cured product obtained from the diepoxy compound is useful because it has excellent thermal conductivity.

Claims (9)

  1. 　式（１）で表わされるジエポキシ化合物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１～Ｒ１２はそれぞれ独立して、水素原子又は炭素数１～３のアルキル基を表わし、Ｑは酸素原子またはメチレン基を表す。ｎは１～３の整数を表す。）     A diepoxy compound represented by the formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer of 1 to 3).
  2. 　式（２）で表わされるジヒドロキシ化合物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ１～Ｒ１２はそれぞれ独立して、水素原子又は炭素数１～３のアルキル基を表わし、Ｑは酸素原子またはメチレン基を表す。ｎは１～３の整数を表す。）     A dihydroxy compound represented by the formula (2).
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q represents an oxygen atom or a methylene group, and n represents an integer of 1 to 3).
  3. 　式（１）で表わされるジエポキシ化合物及び硬化剤を含む組成物。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ１～Ｒ１２はそれぞれ独立して、水素原子又は炭素数１～３のアルキル基を表わし、Ｑは酸素原子またはメチレン基を表す。）     A composition comprising a diepoxy compound represented by formula (1) and a curing agent.
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 1 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q represents an oxygen atom or a methylene group.)
  4. 　さらに、アルミナを含む請求項３に記載の組成物。 The composition according to claim 3, further comprising alumina.
  5. 　アルミナが、２μｍ以上１００μｍ以下のＤ５０を有するアルミナ粒子Ａと、１μｍ以上１０μｍ以下のＤ５０を有するアルミナ粒子Ｂと、０．０１μｍ以上５μｍ以下のＤ５０を有するアルミナ粒子Ｃとを含む請求項４に記載の組成物。Ｄ５０とは、重量累積粒度分布の微粒子側からの累積体積５０％の粒子径を意味する。 5. The alumina according to claim 4, wherein the alumina includes alumina particles A having D50 of 2 μm to 100 μm, alumina particles B having D50 of 1 μm to 10 μm, and alumina particles C having D50 of 0.01 μm to 5 μm. Composition. D50 means a particle diameter of 50% cumulative volume from the fine particle side of the weight cumulative particle size distribution.
  6. 　アルミナの体積を１００体積％としたとき、アルミナに含まれる、アルミナ粒子Ａの含有量が５０～９０体積％であり、アルミナ粒子Ｂの含有量が５～４０体積％であり、アルミナ粒子Ｃの含有量が１～３０体積％である請求項５に記載の組成物。 When the volume of alumina is 100% by volume, the content of alumina particles A contained in alumina is 50 to 90% by volume and the content of alumina particles B is 5 to 40% by volume. The composition according to claim 5, wherein the content is 1 to 30% by volume.
  7. 　請求項３～６のいずれか記載の組成物を基材に塗布もしくは含浸した後、半硬化して得られるプリプレグ。 A prepreg obtained by applying or impregnating a composition according to any one of claims 3 to 6 to a substrate and then semi-curing it.
  8. 　請求項３～６のいずれか記載の組成物を硬化して得られる硬化物。 A cured product obtained by curing the composition according to any one of claims 3 to 6.
  9. 　アルミナを５０～８０体積％含有することを特徴とする請求項８記載の硬化物。 The cured product according to claim 8, which contains 50 to 80% by volume of alumina.
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US11208541B2 (en) 2017-07-28 2021-12-28 Toray Industries, Inc. Prepreg and carbon fiber reinforced material
JP7206910B2 (en) 2017-07-28 2023-01-18 東レ株式会社 Prepregs and carbon fiber reinforced composites

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