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WO2015125674A1 - Composé diépoxy et composition contenant ce composé - Google Patents

Composé diépoxy et composition contenant ce composé 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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WO
WIPO (PCT)
Prior art keywords
epoxypropoxy
cyclohexyl
compound
alumina
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/053683
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English (en)
Japanese (ja)
Inventor
武史 原
義彦 岩永
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Filing date
Publication date
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Publication of WO2015125674A1 publication Critical patent/WO2015125674A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un composé diépoxy représenté par la formule (1). (Dans cette formule, R1 à R12 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle ayant 1-3 atomes de carbone, Q représente un atome d'oxygène ou un groupe méthylène, et n représente un nombre entier de 1 à 3).
PCT/JP2015/053683 2014-02-20 2015-02-10 Composé diépoxy et composition contenant ce composé Ceased WO2015125674A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2017221810A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Matériau barrière au gaz, composition de résine, matière barrière au gaz, produit durci, et matériau composite
WO2017221811A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Composition de résine époxy, produit durci, et matériau composite
WO2019021613A1 (fr) * 2017-07-28 2019-01-31 東レ株式会社 Préimprégné et matériau composite renforcé par fibres de carbone

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JP2011219737A (ja) * 2010-03-23 2011-11-04 Sumitomo Chemical Co Ltd ジエポキシ化合物、該化合物を含む組成物及び該組成物を硬化して得られる硬化物
JP2012131759A (ja) * 2010-12-24 2012-07-12 Sumitomo Chemical Co Ltd ジエポキシ化合物及びその製造方法
JP2012131960A (ja) * 2010-12-24 2012-07-12 Sumitomo Chemical Co Ltd ジエポキシ化合物及びその製造方法

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JP2011219737A (ja) * 2010-03-23 2011-11-04 Sumitomo Chemical Co Ltd ジエポキシ化合物、該化合物を含む組成物及び該組成物を硬化して得られる硬化物
JP2012131759A (ja) * 2010-12-24 2012-07-12 Sumitomo Chemical Co Ltd ジエポキシ化合物及びその製造方法
JP2012131960A (ja) * 2010-12-24 2012-07-12 Sumitomo Chemical Co Ltd ジエポキシ化合物及びその製造方法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017221810A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Matériau barrière au gaz, composition de résine, matière barrière au gaz, produit durci, et matériau composite
WO2017221811A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Composition de résine époxy, produit durci, et matériau composite
CN109328203A (zh) * 2016-06-22 2019-02-12 日立化成株式会社 阻气材料、树脂组合物、阻气材、固化物以及复合材料
CN109415490A (zh) * 2016-06-22 2019-03-01 日立化成株式会社 环氧树脂组合物、固化物和复合材料
JPWO2017221811A1 (ja) * 2016-06-22 2019-03-14 日立化成株式会社 エポキシ樹脂組成物、硬化物及び複合材料
JPWO2017221810A1 (ja) * 2016-06-22 2019-04-11 日立化成株式会社 ガスバリア材料、樹脂組成物、ガスバリア材、硬化物、及び複合材料
WO2019021613A1 (fr) * 2017-07-28 2019-01-31 東レ株式会社 Préimprégné et matériau composite renforcé par fibres de carbone
JPWO2019021613A1 (ja) * 2017-07-28 2020-05-28 東レ株式会社 プリプレグおよび炭素繊維強化複合材料
US11208541B2 (en) 2017-07-28 2021-12-28 Toray Industries, Inc. Prepreg and carbon fiber reinforced material
JP7206910B2 (ja) 2017-07-28 2023-01-18 東レ株式会社 プリプレグおよび炭素繊維強化複合材料

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