WO2011078099A1 - Composé diépoxy, son procédé de préparation et compositions contenant le composé diépoxy - Google Patents

Composé diépoxy, son procédé de préparation et compositions contenant le composé diépoxy Download PDF

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Publication number
WO2011078099A1
WO2011078099A1 PCT/JP2010/072843 JP2010072843W WO2011078099A1 WO 2011078099 A1 WO2011078099 A1 WO 2011078099A1 JP 2010072843 W JP2010072843 W JP 2010072843W WO 2011078099 A1 WO2011078099 A1 WO 2011078099A1
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alumina
formula
curing agent
composition
epoxypropoxy
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PCT/JP2010/072843
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English (en)
Japanese (ja)
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武史 原
拓 浅海
板垣　誠
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—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
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings

Definitions

  • the present invention relates to a diepoxy compound, a production method thereof, and a composition containing the diepoxy compound.
  • the present invention [1] Formula (1) (In the formula, R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
  • a dihydroxy compound represented by the formula (3) In the formula, X 1 represents a halogen atom.
  • Comprising the step of reacting with an epihalohydrin represented by formula (1) In the formula, R 1 , R 2 , R 3 and R 4 have the same meaning as described above.
  • the diepoxy compound of the present invention has the formula (1) (In the formula, R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Indicated by Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • diepoxy compound (1) As the diepoxy compound represented by formula (1) (hereinafter abbreviated as diepoxy compound (1)), diepoxy compound (1), wherein R 1 , R 2 , R 3 and R 4 are hydrogen atoms, R 1 and R 2 is the same alkyl group having 1 to 3 carbon atoms, R 3 and R 4 are hydrogen atoms and diepoxy compound (1), and R 1 and R 4 are the same alkyl group having 1 to 3 carbon atoms
  • a diepoxy compound (1) in which R 2 and R 3 are hydrogen atoms is preferred.
  • the diepoxy compound (1) is represented by the formula (2) in the presence of an inorganic base.
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a dihydroxy compound hereinafter abbreviated as compound (2)
  • formula (3) In the formula, X 1 represents a halogen atom.
  • process (I) which reacts with the epihalohydrin shown below (it abbreviates as epihalohydrin (3) hereafter).
  • X 1 in the epihalohydrin (3) represents a halogen atom, and examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is preferable.
  • Epihalohydrin (3) includes epichlorohydrin and epibromohydrin. Two or more kinds of epihalohydrins (3) may be used in combination.
  • the amount of epihalohydrin (3) to be used is generally 2-200 mol, preferably 5-150 mol, per 1 mol of compound (2).
  • inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrogens such as sodium hydride and potassium hydride.
  • alkali metal hydroxides are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
  • Two or more inorganic bases may be used in combination.
  • the amount of the inorganic base to be used is generally 0.1 to 20 mol, preferably 0.5 to 10 mol, per 1 mol of compound (2).
  • An inorganic base in a solid form such as a granular material can be used.
  • an inorganic base that is stable to water such as an alkali metal hydroxide or an alkali metal carbonate
  • an aqueous solution having a concentration of about 1 to 60% by weight can be used.
  • the reaction of compound (2) and epihalohydrin (3) is preferably carried out in the presence of an ammonium salt in addition to the inorganic base.
  • ammonium salts tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltrimethyl Quaternary ammonium halides such as ammonium bromide, benzyltriethylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, benzyltributylammonium iodide, and the like are preferred.
  • Moniumuburomido and benzyl bromide is more preferable.
  • Two or more ammonium salts may be used in combination.
  • the amount of the ammonium salt to be used is generally 0.0001 to 1 mol, preferably 0.001 to 0.5 mol, per 1 mol of compound (2).
  • the reaction between compound (2) and epihalohydrin (3) is preferably carried out in the presence of an aliphatic alcohol.
  • Examples of the aliphatic alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 2-octanol, 4-decanol, 2-dodecanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 3-methyl-2-pentanol, 5-methyl 2-hexanol, 4-methyl-3-heptanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3- Methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3-dimethyl Examples include ru-3-pentanol, 3-e
  • aliphatic secondary alcohols and aliphatic tertiary alcohols having 4 to 12 carbon atoms Preferred are aliphatic secondary alcohols and aliphatic tertiary alcohols having 4 to 12 carbon atoms, and more preferred are aliphatic tertiary alcohols having 4 to 10 carbon atoms.
  • Two or more aliphatic alcohols may be used in combination.
  • the amount of the aliphatic alcohol used is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 50 parts by weight with respect to 1 part by weight of the compound (2). It is.
  • the reaction of compound (2) and epihalohydrin (3) may be performed without a solvent or in the presence of a solvent.
  • Solvents include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile and dimethyl sulfoxide, diethyl ether , Tert-butyl methyl ether, 1,2-dimethoxyethane, 1,4-dioxane, tetrahydrofuran, anisole and other ether solvents and chloroform, dichloromethane, 1,2-dibromoethane and other halogenated hydrocarbon solvents, N , N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are preferred.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • Two or more solvents may be used in combination.
  • the amount of the solvent to be used is generally 0.01-100 parts by weight, preferably 0.1-50 parts by weight, per 1 part by weight of compound (2).
  • the reaction between the compound (2) and the epihalohydrin (3) may be performed under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. You may implement reaction in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction of compound (2) with epihalohydrin (3) is usually carried out by mixing compound (2), epihalohydrin (3), an inorganic base, and, if necessary, an ammonium salt, an aliphatic alcohol and a solvent. Is done.
  • the reaction temperature is usually ⁇ 20 ° C.
  • Step (I) preferably includes the following steps (i) and (ii).
  • Step (i) Step of mixing compound (2), epihalohydrin (3) and ammonium salt
  • Step (ii) Step of mixing the mixture obtained in step (i) and an inorganic base. Step (i) may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions.
  • the reaction temperature in step (i) is usually ⁇ 10 ° C. to 150 ° C., preferably 0 ° C. to 120 ° C.
  • the reaction time in step (i) varies depending on the reaction temperature, but is usually 0.5 to 72 hours.
  • Step (ii) may be performed under normal pressure conditions, may be performed under pressure conditions, or may be performed under reduced pressure conditions.
  • Step (ii) may be performed under an inert gas atmosphere such as nitrogen gas or argon gas.
  • the reaction temperature in step (ii) is usually ⁇ 20 ° C. to 120 ° C., preferably ⁇ 10 ° C. to 80 ° C.
  • Step (ii) is preferably carried out until no increase in the amount of diepoxy compound (1) is confirmed, and the reaction time is usually 0.5 to 72 hours, although it varies depending on the reaction temperature.
  • an organic layer containing the diepoxy compound (1) is obtained by mixing the reaction mixture, water, and, if necessary, a solvent insoluble in water and separating the liquid.
  • the obtained organic layer is washed with water, for example, and then the insoluble matter is removed by filtration as necessary, followed by concentration, whereby the diepoxy compound (1) can be taken out.
  • the taken-out diepoxy compound (1) can be further purified by ordinary purification means such as recrystallization.
  • Water-insoluble solvents include halogenated hydrocarbon solvents such as dichloromethane, chloroform, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate and butyl acetate, and aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene and mesitylene.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and the amount used is usually 1 to 300 parts by weight, preferably 10 to 200 parts by weight, per 1 part by weight of the diepoxy compound (1).
  • the diepoxy compound (1) is prepared by mixing the compound (2) with the formula (4) (In the formula, X 2 represents a halogen atom.) Is reacted with a compound represented by formula (5) (hereinafter abbreviated as compound (4)). (In the formula, R 1 , R 2 , R 3 and R 4 have the same meaning as described above.) (Hereinafter abbreviated as compound (5)), and the compound (5) obtained can be produced by a method of oxidizing with an oxidizing agent.
  • X 2 in the compound (4) represents a halogen atom, and examples of the halogen atom include a chlorine atom and a bromine atom.
  • Compound (4) includes allyl chloride and allyl bromide.
  • the amount of compound (4) to be used is generally 2-200 mol, preferably 2-100 mol, per 1 mol of compound (2).
  • the base may be an inorganic base or an organic base, and an inorganic base is preferable.
  • the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate.
  • the organic base include pyridine. Among these, alkali metal carbonates are preferable, and sodium carbonate and potassium carbonate are more preferable.
  • Two or more bases may be used in combination. When an inorganic base is used, the amount used is usually 2 to 10 mol per 1 mol of compound (2).
  • the amount used is 1 mol per compound (2). Usually 2 moles or more.
  • the organic base may also be used as a solvent in a large excess amount.
  • the reaction between compound (2) and compound (4) is preferably performed in a solvent. Examples of the solvent include the same solvents as those used in the reaction of the aforementioned compound (2) and epihalohydrin (3).
  • the organic base may be used as a solvent. Reaction of a compound (2) and a compound (4) is normally implemented by mixing a compound (2), a compound (4), a base, and a solvent as needed, The mixing order is not restrict
  • the reaction may be carried out under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. Moreover, you may react in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction temperature is usually ⁇ 20 ° C. to 120 ° C., preferably ⁇ 10 ° C. to 100 ° C.
  • the progress of the reaction can be confirmed by ordinary analytical means such as liquid chromatography, and it is preferable to carry out the reaction until no increase in the amount of compound (5) produced is observed.
  • the obtained reaction mixture containing the compound (5) is usually mixed with an oxidizing agent as it is or after being washed with water, and the reaction between the compound (5) and the oxidizing agent is carried out.
  • the oxidizing agent may be any oxidizing agent that can convert a carbon-carbon double bond to an epoxy group, and specific examples thereof include peracids such as m-chloroperbenzoic acid.
  • the amount of the oxidizing agent to be used is generally 2 to 20 mol per 1 mol of compound (5).
  • the reaction between the compound (5) and the oxidizing agent may be performed under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. Moreover, you may react in inert gas atmosphere, such as nitrogen gas and argon gas.
  • the reaction temperature is usually ⁇ 20 ° C. to 120 ° C., preferably ⁇ 10 ° C. to 100 ° C.
  • the progress of the reaction can be confirmed by ordinary analytical means such as liquid chromatography, and it is preferable to carry out the reaction until no increase in the amount of diepoxy compound (1) is observed.
  • the reaction time is usually 0.5 to 72 hours.
  • the diepoxy compound (1) can be taken out by concentrating the reaction mixture. After decomposing the oxidizing agent remaining in the reaction mixture, concentration may be performed. The taken-out diepoxy compound (1) can be further purified by ordinary purification means such as recrystallization.
  • Compound (2) is, for example, a method of reacting 2-hydroxy-6-naphthoic acid with hydroquinone in the presence of an acid described in US2008 / 0221289A1, or a compound represented by formula (6) (Wherein R 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X 3 represents a halogen atom.) And a compound of formula (7) (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as described above.) And a product obtained by reacting the resulting product with a primary amine or ammonia.
  • composition X containing diepoxy compound (1) and a hardening
  • the composition X can contain 2 or more types of diepoxy compounds (1).
  • the composition X can contain 2 or more types of hardening
  • the composition X can contain a solvent in addition to the diepoxy compound (1) and the curing agent. In terms of easy preparation, the composition X preferably contains a solvent.
  • the solvent examples 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. And the like, and a ketone solvent is preferable, and methyl isobutyl ketone is more preferable. Since the diepoxy compound (1) of the present invention has a low melting point, the diepoxy compound (1) obtained even if the solvent is removed from the solution obtained by dissolving the diepoxy compound (1) and the curing agent in the solvent.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone
  • Precipitation of diepoxy compound (1) tends to be suppressed from a mixture of a curing agent and a curing agent. Moreover, even if it removes the said solvent from the mixture obtained by mixing diepoxy compound (1), a hardening
  • Any curing agent may be used as long as it has at least one functional group capable of undergoing a curing reaction with the epoxy group in the diepoxy compound (1) or exhibits a catalytic action in the curing reaction of the diepoxy compound (1).
  • an amine curing agent in which the functional group is an amino group a phenol curing agent in which the functional group is a hydroxyl group, and an acid anhydride curing agent in which the functional group is a group represented by -CO-O-CO- And curing catalysts, with amine curing agents, phenol curing agents and curing catalysts being preferred.
  • amine curing agents include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and other aliphatic polyamines having 2 to 20 carbon atoms, p-xylenediamine, m-xylenediamine, 1 , 5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, Aromatic polyamines such as 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylsulfone, bis (4-aminophenyl) phenylmethane, 4,4′
  • aromatic polyamines and dicyandiamide are preferable, and 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene, p-phenylenediamine and dicyandiamide are more preferable.
  • the phenol curing agent include a phenol resin, a phenol aralkyl resin (having a phenylene skeleton, a diphenylene skeleton, etc.), a naphthol aralkyl resin, and a polyoxystyrene resin.
  • phenol resin examples include resol type phenol resins such as aniline-modified resole resin and dimethyl ether resole resin, novolac type phenol resins such as phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, nonylphenol novolac resin, and dicyclopentadiene modified. Special phenol resins such as phenol resin, terpene-modified phenol resin, and triphenolmethane type resin can be mentioned.
  • 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 anhydride and 5- (2,5-dioxo Tetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
  • Examples of the curing catalyst include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and benzyldimethylamine. What is necessary is just to select the usage-amount of a hardening
  • the total number of moles of functional groups capable of undergoing a curing reaction with the epoxy group in the curing agent is 0.5 to 1 mole per 1 mole of the epoxy group in the diepoxy compound (1).
  • a curing agent is used in an amount of 1.5 mol, preferably 0.9 to 1.1 mol.
  • the composition X has a desired performance of the cured product obtained by curing the composition X (for example, solubility, heat resistance, thermal conductivity, etc.). As long as it does not cause a decrease, compounds having other epoxy groups can be included.
  • composition X can contain various additives in addition to the diepoxy compound (1), the curing agent and the solvent.
  • Additives include curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, 2-phenylimidazole; coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane 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 or metal salt thereof, paraffin; antioxidant; fused crushed silica powder, fused sphere Silica such as silica powder, crystalline silica powder, secondary agglomerated silica powder; alumina such as ⁇ -alumina or transition alumina ( ⁇ -alumina, ⁇ -alumina, ⁇ -alumina); titanium white; aluminum hydroxide; talc; clay; Mica; and glass fiber.
  • curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, 2-phenylimidazole
  • the composition X can contain an additive in an amount that does not cause a decrease in the desired performance (eg, melting point) of the cured product obtained by curing the composition X.
  • the composition X preferably contains alumina from the viewpoint of improving the thermal conductivity of a cured product obtained by curing the composition X.
  • curing agent, and an alumina is preferable, and it is preferable that the composition X further contains an above-described solvent at the point that the preparation is easy.
  • the content of alumina is usually 75 parts by weight to 95 parts by weight, preferably 83 parts per 100 parts by weight in total of the diepoxy compound (1), the curing agent and alumina. Parts by weight to 90 parts by weight.
  • the composition containing 75 parts by weight or more of alumina with respect to a total of 100 parts by weight of the diepoxy compound (1), the curing agent and alumina improves the thermal conductivity of the cured product obtained by curing the composition.
  • the composition in which the amount of alumina is 95 parts by weight or less tends to be easily formed.
  • alumina granular alumina is preferable, and D50 is 2 ⁇ m or more and 100 ⁇ m or less, where D50 is the particle size of 50% cumulative volume from the fine particle side of the weight cumulative particle size distribution (average particle size measured by laser diffraction method). More preferred is alumina which is a mixture of certain alumina A, alumina B having a D50 of 1 ⁇ m or more and 10 ⁇ m or less, and alumina C having a D50 of 0.01 ⁇ m or more and 5 ⁇ m or less.
  • each alumina in the total volume of 100% by volume of alumina A, alumina B and alumina C is 50 to 90% by volume for alumina A, 5 to 40% by volume for alumina B, and 1 to 30% by volume for alumina C. It is preferable that Such alumina can be prepared, for example, by appropriately mixing commercially available alumina having various average particle sizes. Further, the content ratio of alumina contained in the cured product is preferably 50 to 80% by volume, more preferably 60 to 74% by volume with respect to 100% by volume of the cured product.
  • a method for producing a cured product obtained by curing the composition X a method of curing the composition X by heating to a predetermined temperature, a composition X is heated and melted and poured into a mold or the like, and the mold is further A method of molding by heating, a method of melting the composition X, a method of injecting and curing the resulting melt into a preheated mold, a partial curing of the composition X, and pulverizing the resulting partially cured product, After filling the obtained powder into a mold, melt-molding the filled powder, and dissolving the composition X in a solvent as necessary, partially curing while stirring, and casting the resulting solution A method of drying by 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 required.
  • the substrate is applied or impregnated, and then the obtained substrate is heated to semi-cure the diepoxy compound (1) in the substrate.
  • a prepreg can also be manufactured.
  • a laminate can be obtained by laminating a plurality of prepregs and applying pressure and heating with a press or the like.
  • the base material used for 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.
  • a cured product obtained by curing the composition X Is excellent in thermal conductivity, and a cured product obtained by curing the composition X containing alumina is further excellent in thermal conductivity.
  • the resulting mixture was stirred at 70 ° C. for 6 hours and then cooled to room temperature.
  • the resulting mixture was concentrated under reduced pressure. 200 mL of methanol was added to the obtained residue. After stirring the resulting mixture, the solid was removed by filtration. The extracted solid, 300 mL of chloroform, and 76.13 g of a 15 wt% aqueous sodium hydroxide solution were mixed. The resulting mixture was stirred at room temperature for 3 hours.
  • 200 mL of ion-exchanged water was added, and after stirring, the organic layer and the aqueous layer were separated. The organic layer was washed with 200 mL of ion exchange water three times and then concentrated to obtain a crude product.
  • the obtained powdery composition was filled in an alumina pan.
  • the alumina pan filled with the composition was heated with a differential scanning calorimeter (DSC Q2000 manufactured by TA Instruments) to obtain a cured product (curing condition: heated at 140 ° C. for 20 minutes in a nitrogen atmosphere, then 180 ° C. Until heating at 1 ° C./min, and further heating at 200 ° C. for 30 minutes).
  • the obtained cured product was cooled to 20 ° C.
  • the glass transition point of the cured product was measured with a differential scanning calorimeter (temperature increase rate: 20 ° C./min, measurement temperature range: room temperature to 200 ° C.), it was 174 ° C.
  • Example 9 In Example 6, instead of 25 parts by weight of 4,4′-diaminodiphenylmethane, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (Tokyo) This was carried out in the same manner as in Example 6 except that 33 parts by weight of Kasei Kogyo Co., Ltd. and 2.6 parts by weight of 2-phenylimidazole were further used as a curing accelerator, to obtain a solution-like composition.
  • Tokyo 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride
  • the obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product. The glass transition point of the cured product was 134 ° C.
  • Example 6 The obtained powdery composition was heated in the same manner as in Example 6 to obtain a cured product.
  • the glass transition point of the cured product was 106 ° C.
  • Example 11 In Example 6, instead of 25 parts by weight of 4,4′-diaminodiphenylmethane, 10 parts by weight of dicyandiamide (Wako Pure Chemical Industries, Ltd.) was used, and 2.2 parts by weight of 2-phenylimidazole was further added as a curing accelerator. Except having used, it implemented similarly to Example 6 and obtained the solution-form composition. The obtained solution-like composition was concentrated with a centrifugal concentrator to obtain a uniform powdery composition.
  • the prepared composition was applied onto a polyethylene terephthalate (PET) film with an applicator so as to have a thickness of 350 ⁇ m.
  • PET polyethylene terephthalate
  • the obtained sheet was sandwiched between aluminum foils having a thickness of 40 ⁇ m, and vacuum press molding (press condition: vacuum degree 1 kPa, press pressure 6 MPa, 150 ° C., 20 minutes) was performed.
  • the press temperature was raised to 180 ° C. over 40 minutes, and vacuum press molding was performed.
  • the aluminum foil was peeled off to obtain a sheet-like cured product having a thickness of 317 ⁇ m.
  • the content ratio of the alumina powder in the obtained cured product was calculated, and the alumina powder in the cured product was calculated.
  • the content ratio of was 74% by volume.
  • (Alumina powder A1 / Alumina powder B1 / Alumina powder C1) Prepared by mixing at 74/14/12) and as solvent Mixed with 430 parts by weight of methyl isobutyl ketone, N, and N- dimethylformamide 12 parts by weight, to prepare a composition.
  • PET polyethylene terephthalate
  • Example 12 the obtained sheet was subjected to vacuum press molding to obtain a sheet-like cured product having a thickness of 343 ⁇ m.
  • the thermal conductivity of the cured product was measured in the same manner as in Example 12, it was 9.6 W / (m ⁇ K).
  • the content of alumina powder in the cured product was 74% by volume.
  • a solution-like composition can be prepared by mixing 380 parts by weight of methyl isobutyl ketone and 70 parts by weight of N, N-dimethylformamide as a solvent.
  • a prepreg can be obtained by impregnating a 0.2 mm-thick glass fiber woven fabric with the resulting composition and then heating.
  • a laminate can be obtained by stacking four prepregs obtained and press-molding at 175 ° C.
  • alumina powder ⁇ -alumina powder manufactured by Sumitomo Chemical Co., Ltd .
  • D50 average particle diameter
  • the diepoxy compound of the present invention has a low melting point, it is easy to handle, and a cured product obtained by curing a composition containing the diepoxy compound has high thermal conductivity.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne un composé diépoxy représenté par la formule générale (1) [dans laquelle R1, R2, R3 et R4 sont chacun indépendamment un atome d'hydrogène ou un alkyle en C1-3].
PCT/JP2010/072843 2009-12-25 2010-12-14 Composé diépoxy, son procédé de préparation et compositions contenant le composé diépoxy WO2011078099A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112794829A (zh) * 2019-11-14 2021-05-14 三星电子株式会社 环氧化合物、组合物、用于半导体封装的材料、模塑产品、电气和电子器件及半导体封装
CN114379111A (zh) * 2022-01-14 2022-04-22 东莞市华创碳纤维科技有限公司 一种温度可控的玻璃纤维自动固化工艺
CN116063252A (zh) * 2022-12-26 2023-05-05 北京智芯微电子科技有限公司 联萘单体及其制备方法和环氧树脂及其制备方法和应用

Citations (4)

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Publication number Priority date Publication date Assignee Title
WO1992019583A1 (fr) * 1991-05-02 1992-11-12 Centre International De Recherches Dermatologiques Galderma (Cird Galderma) Nouveaux composes polycycliques aromatiques et leur utilisation en medecine humaine ou veterinaire et en cosmetique
JP2001181268A (ja) * 1999-12-27 2001-07-03 Asahi Kasei Corp 脂環式エポキシ化合物及びその組成物
WO2006120220A1 (fr) * 2005-05-11 2006-11-16 Basf Aktiengesellschaft Composes contenant des groupes 2,6-naphthyle
WO2007120458A1 (fr) * 2006-03-31 2007-10-25 E. I. Du Pont De Nemours And Company Compositions à base de cristaux liquides, réseaux polymères ainsi obtenus et procédé de préparation associé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992019583A1 (fr) * 1991-05-02 1992-11-12 Centre International De Recherches Dermatologiques Galderma (Cird Galderma) Nouveaux composes polycycliques aromatiques et leur utilisation en medecine humaine ou veterinaire et en cosmetique
JP2001181268A (ja) * 1999-12-27 2001-07-03 Asahi Kasei Corp 脂環式エポキシ化合物及びその組成物
WO2006120220A1 (fr) * 2005-05-11 2006-11-16 Basf Aktiengesellschaft Composes contenant des groupes 2,6-naphthyle
WO2007120458A1 (fr) * 2006-03-31 2007-10-25 E. I. Du Pont De Nemours And Company Compositions à base de cristaux liquides, réseaux polymères ainsi obtenus et procédé de préparation associé

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112794829A (zh) * 2019-11-14 2021-05-14 三星电子株式会社 环氧化合物、组合物、用于半导体封装的材料、模塑产品、电气和电子器件及半导体封装
CN114379111A (zh) * 2022-01-14 2022-04-22 东莞市华创碳纤维科技有限公司 一种温度可控的玻璃纤维自动固化工艺
CN116063252A (zh) * 2022-12-26 2023-05-05 北京智芯微电子科技有限公司 联萘单体及其制备方法和环氧树脂及其制备方法和应用

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