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WO2011142466A1 - Epoxy resin, epoxy resin composition, and cured product thereof - Google Patents

Epoxy resin, epoxy resin composition, and cured product thereof Download PDF

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Publication number
WO2011142466A1
WO2011142466A1 PCT/JP2011/061106 JP2011061106W WO2011142466A1 WO 2011142466 A1 WO2011142466 A1 WO 2011142466A1 JP 2011061106 W JP2011061106 W JP 2011061106W WO 2011142466 A1 WO2011142466 A1 WO 2011142466A1
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WIPO (PCT)
Prior art keywords
epoxy resin
carbon atoms
resin composition
group
formula
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/JP2011/061106
Other languages
French (fr)
Japanese (ja)
Inventor
宏一 川井
克彦 押見
高男 須永
一真 井上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP2012514853A priority Critical patent/JPWO2011142466A1/en
Publication of WO2011142466A1 publication Critical patent/WO2011142466A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
    • 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
    • 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
    • C08G59/20—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to an epoxy resin composition having a low melt viscosity, excellent fluidity, and giving a cured product excellent in flame retardancy, adhesion and heat resistance.
  • Patent Document 1 containing a phenolphthalein type epoxy resin has been reported as an epoxy resin composition that meets the required characteristics of halogen-free, antimony-free, phosphorus-free flame retardant and high heat resistance. It is noted that the product has a flame retardancy of V-0 at UL94 and also exhibits excellent heat resistance.
  • phenolphthalein type epoxy resin has a low viscosity compared with general high heat resistant resin, it is not enough in the packaging field where high fluidity is required, such as packaging, which is remarkably densely packed. However, further reduction in viscosity is necessary.
  • one of the causes of cracks that cause a problem in the package is that the sealing resin is peeled off from the lead frame, and moisture is accumulated in this portion, which expands.
  • package cracks can be prevented by improving the adhesion between the sealing resin and the lead frame.
  • the present invention has been made in view of the above problems in the prior art, and an epoxy resin composition that provides a cured product having a low melt viscosity, excellent fluidity, and excellent flame retardancy, adhesion, and heat resistance.
  • the purpose is to provide.
  • the present invention provides [1] Formula (1) (Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 , and represents an integer of 1 to 4.) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (2) (Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4.
  • A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring.
  • At least any one epoxy resin among the epoxy resins obtained, and Formula (3) (Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.
  • n represents the number of R 3 and R 4 , respectively, and represents an integer of 1 to 4.
  • An epoxy resin composition containing, [2] Formula (1) (Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 and represents an integer of 1 to 4.) and a phenol compound represented by formula (2) (Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4.
  • A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring.
  • One phenolic compound, Formula (3) (Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.
  • n represents the number of R 3 and R 4 , respectively, and represents an integer of 1 to 4.
  • An epoxy resin composition obtained by reacting an epihalohydrin with a mixture containing [3] A mixture of phenol compounds in which the proportion of the phenol compound selected from formulas (1) and (2) is 1 to 30% by mass in the mixture of phenol compounds represented by formulas (1) to (3)
  • the epoxy resin composition according to the above [2] obtained by reacting an epihalohydrin with [4] Curable resin composition comprising the epoxy resin composition according to any one of [1] to [3] above and a curing agent [5]
  • the above [4] containing an inorganic filler Curable resin composition according to [6] A cured product of the curable resin composition according to any one of [4] and [5], [7]
  • the present invention relates to a semiconductor sealing material molded by using the curable resin composition according to any one of [4] and [5].
  • the epoxy resin composition of the present invention is an epoxy resin composition excellent in fluidity while being a resin that gives a cured product excellent in flame retardancy, adhesion to metal and heat resistance. Therefore, the curable resin composition containing the epoxy resin composition of the present invention is useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resist applications, and the like.
  • the epoxy resin composition of the present invention is (Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 , and represents an integer of 1 to 4.) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (2) (Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4.
  • A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring.
  • At least any one epoxy resin among the epoxy resins obtained, and Formula (3) (Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. And n each represents the number of R 3 and R 4 and represents an integer of 1 to 4.) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by
  • phenolic compound represented by Formula (1) Various bisphenols are mentioned as a phenolic compound represented by Formula (1). Specifically, BPF, BPA, BPE, Methylenebis-p-CR, TM-BPF, Bis-C, BisP-MIBK, Bis26X-A, BisP-AP, BisOPP-A, UltimateP, DHBP, BisOC-F, BisP- B, BisP-IBTD, Bis-BA, BisP-IOTD, BisOIPP-A, BisP-DED, BisOSBP-A, BisOTBP-A, Bis2M6B-IBTD, BisOCHP-A, Ph-CC-AP (all manufactured by Honshu Chemical Industry) ) And the like.
  • X and Y are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is particularly preferable. Further, in the above formula (1), R 1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • phenolic compound represented by the formula (2) in addition to a biphenyl having a direct bond at the position A and a 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol compound, Examples thereof include phenol compounds obtained by reacting corresponding cycloaliphatic ketones and phenols.
  • A is preferably a direct bond in the above formula (2).
  • R 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • Specific examples of the phenol compound represented by the formula (2) include the following compounds.
  • the phenol compound is commercially available, for example, BisP-CP, BisP-Z, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisP- TCD, BisOC-CDE, Bis26X-CDE, BisP-CHEP, BisP-COCT, BisP-CPeDE (all manufactured by Honshu Chemical Industry Co., Ltd.), TCDBP (METROPOLITAN EXIMCHEM XTD), and the like.
  • the phenolic compound (phenolphthaleins) represented by the formula (3) can be synthesized generally by reacting phenols and acid anhydrides of phthalic acids under acidic conditions.
  • phenols phenols
  • acid anhydrides of phthalic acids for example, Revistade Chimie (1958), 9,151 -152 “The Synthesis of phenolphtaleine with chlorosulfonic acid as the condensation agent” describes a method for synthesizing phenolphthaleins using chlorosulfonic acid.
  • Specific substituents applicable to R 3 and R 4 include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group).
  • R 3 and R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of easy availability, phenolphthalein is particularly preferable.
  • an epoxy resin may be obtained by previously reacting each phenol compound of the formulas (1) to (3) with an epihalohydrin, and each epoxy resin may be mixed. Absent.
  • any known method can be used without particular limitation, and specific examples thereof include, for example, Japanese Patent Application Laid-Open No. 05-155978 and Japanese Patent Application Laid-Open No. 2008-179739. Can be used.
  • it is preferable to obtain an epoxy resin composition by reacting a mixture of the phenol compounds of formulas (1) to (3) with an epihalohydrin.
  • the amount of the phenols selected from the formulas (1) and (2) in the total amount of the phenolic compounds of the formulas (1) to (3) is desirably 1 to 30% by mass, more preferably 5 to 30% by mass. .
  • the proportion of phenolphthaleins is small, the heat resistance is inferior, and when the proportion is large, the melt viscosity becomes large and the adhesion to metal is inferior.
  • epichlorohydrin, ⁇ -methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, and in the present invention, epichlorohydrin which is easily available industrially is preferable.
  • the amount of epihalohydrin used is usually 2 to 20 mol, preferably 4 to 10 mol, per mol of hydroxyl group in the mixture of phenol compounds of formulas (1) to (3).
  • an alkali metal hydroxide is used.
  • the alkali metal hydroxide that can be used include sodium hydroxide and potassium hydroxide.
  • the alkali metal hydroxide may be a solid or an aqueous solution thereof.
  • the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, followed by liquid separation to remove the water.
  • the epihalohydrin may be continuously returned to the reaction system.
  • the amount of the alkali metal hydroxide to be used is usually 0.8 to 2.0 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1 mol of the hydroxyl group of the phenol compound of the present invention. ⁇ 1.5 moles.
  • a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst.
  • the amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol compound of the present invention.
  • reaction it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.
  • aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.
  • the amount used is usually 2 to 50% by weight, preferably 4 to 20% by weight, based on the amount of epihalohydrin used.
  • an aprotic polar solvent is used, it is usually 5 to 100% by weight, preferably 10 to 80% by weight, based on the amount of epihalohydrin used.
  • the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C.
  • the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.
  • the reaction product is washed with water or without washing with water, and the epihalohydrin, the solvent and the like are removed under heating and reduced pressure.
  • the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. Can react to ensure ring closure.
  • the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of the hydroxyl group of the phenol compound of the present invention.
  • the reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
  • the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin composition of the present invention.
  • each phenol compound of formulas (1) to (3) is obtained.
  • Each of the epoxy resins may be mixed after previously reacting with epihalohydrin to obtain an epoxy resin.
  • the amount of the epoxy resin derived from the phenol compound selected from the formulas (1) and (2) in the total amount of the epoxy resin derived from each phenol compound of the formulas (1) to (3) is 1 to 30% by mass. More preferably, the content is 5 to 30% by mass.
  • the curable resin composition of the present invention contains the epoxy resin composition of the present invention and a curing agent as essential components.
  • the epoxy resin composition of the present invention can be used alone or in combination with other epoxy resins.
  • the proportion of the epoxy resin composition of the present invention in the total epoxy resin is preferably 30% by mass or more, particularly preferably 40% by mass or more.
  • the epoxy resin composition of the present invention is used as a modifier for the curable resin composition, it is added at a ratio of 1 to 30% by mass.
  • bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde (o- or p-), hydroxyacetophenone (o- or p- , Dicyclopenta
  • curing agent contained in the curable resin composition of the present invention examples include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds.
  • curing agents that can be used include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and isophoronediamine; amides such as polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine.
  • phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.
  • Carboxylic acid compounds bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5 5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4 -Hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde (o- or p-), hydroxyacetophenone (o- Or p-), dicycl
  • the amount of the curing agent used is 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin component (the epoxy resin composition of the present invention and other epoxy resins). preferable. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
  • a curing accelerator (curing catalyst) may be used.
  • curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane, and metal compounds such as tin octylate.
  • the curing accelerator is used in an amount of 0.02 to 5.0 parts by mass based on 100 parts by mass of the epoxy resin component, if necessary.
  • an inorganic filler can be added to the curable resin composition of the present invention as necessary.
  • Inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, barium sulfate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, clay, Examples include magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, titanium oxide, aluminum nitride, silicon nitride, boron nitride, mica, glass, quartz, and mica powder, or beads made from these. It is not limited. These may be used alone or in combination of two or more.
  • an amount occupying 0 to 95% by mass in the curable composition of the present invention is used.
  • it is particularly preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of flame retardancy and mechanical strength.
  • a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable composition of the present invention. be able to.
  • a release agent can be blended to improve the release from the mold during molding.
  • Any conventionally known release agent can be used as the release agent.
  • ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, polyethylene oxide, non-oxidized polyethylene, etc.
  • examples include polyolefin wax. These may be used alone or in combination of two or more.
  • the compounding amount of these release agents is preferably 0.1% by mass to 3% by mass with respect to all organic components.
  • a coupling agent can be blended in order to improve the adhesion between the inorganic filler and the resin component.
  • Any conventionally known coupling agent can be used.
  • examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more.
  • the coupling agent may be added by treating the surface of the inorganic filler with the coupling agent in advance and then kneading with the resin, or mixing the coupling agent with the resin and then kneading with the inorganic filler. .
  • the curable resin composition of the present invention can contain known additives as required.
  • additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, and silicone oil.
  • colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
  • the curable resin composition of the present invention can be produced using any conventionally known technique capable of uniformly dispersing and mixing each component. For example, all the components are pulverized and mixed with a Henschel mixer or the like, then melt kneaded with a heating roll, melt kneaded with a kneader, mixed with a special mixer, or an appropriate combination of these methods.
  • the semiconductor device of the present invention can be manufactured by resin-sealing a semiconductor element mounted on a lead frame or the like by transfer molding or the like using the curable resin composition of the present invention.
  • the semiconductor device of the present invention has a cured product of the curable resin composition of the present invention such as one sealed with the curable resin composition of the present invention.
  • semiconductor devices for example, DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package).
  • DIP Dual Inline Package
  • QFP Quad Flat Package
  • BGA Bit Grid Array
  • CSP Chip Size Package
  • SOP Small Outline Package
  • TSOP Thin Small Outline Package
  • TQFP Seink Quad Flat Package
  • the copper-based lead frame is a lead frame made of a copper alloy and subjected to various plating processes.
  • Example 1 While purging a flask equipped with a stirrer, a reflux condenser, and a stirrer with nitrogen purge, 120 parts of phenolphthalein, 30 parts of biphenol, 597 parts of epichlorohydrin, 124 parts of dimethyl sulfoxide, and 9 parts of water were added and stirred at 45 ° C. The solution was heated to 50 ° C., and 47 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by stirring at 45 ° C. for 120 minutes, 60 ° C. for 120 minutes, and 70 ° C. for 60 minutes. After completion of the reaction, excess epichlorohydrin and the like were distilled off from the oil layer under reduced pressure at 130 ° C.
  • the epoxy resin composition obtained had an epoxy equivalent of 222 g / eq, a JIS softening point of 87 ° C., and an ICI melt viscosity at 150 ° C. of 0.05 Pa ⁇ s.
  • Example 2 198 parts of an epoxy resin composition (E2) was obtained in the same manner as in Example 1 except that 145 parts were used for 120 parts of phenolphthalein and 16 parts of bisphenol F were used for 30 parts of biphenol.
  • the epoxy resin composition obtained had an epoxy equivalent of 234 g / eq, a JIS softening point of 58 ° C., and an ICI melt viscosity at 150 ° C. of 0.07 Pa ⁇ s.
  • Example 3 An epoxy resin composition (E3) (204 parts) was obtained in the same manner as in Example 1 except that 160 parts of phenolphthalein and 160 parts of phenolphthalein and 8.4 parts of bisphenol A were used.
  • the obtained epoxy resin composition had an epoxy equivalent of 233 g / eq, a JIS softening point of 65 ° C., and an ICI melt viscosity at 150 ° C. of 0.10 Pa ⁇ s.
  • Example 4 An epoxy resin composition (E4) 214 parts was obtained in the same manner as in Example 1 except that 136 parts of phenolphthalein was used and 136 parts of biphenol 30 were used 34 parts of bisphenol I.
  • the epoxy resin composition obtained had an epoxy equivalent of 227 g / eq, a JIS softening point of 62 ° C., and an ICI melt viscosity at 150 ° C. of 0.07 Pa ⁇ s.
  • Comparative Example 1 Using 171 parts of Example 1 and 120 parts of phenolphthalein, and performing the same operation except not using biphenol, 219 parts of an epoxy resin composition (E5) was obtained.
  • the epoxy equivalent of the obtained epoxy resin composition was 240 g / eq
  • the JIS softening point was 68 ° C.
  • the ICI melt viscosity at 150 ° C. was 0.11 Pa ⁇ s.
  • Examples 5 to 8 and Comparative Example 2 Various components were blended in the proportions (parts by weight) shown in Table 1, kneaded with a mixing roll, tableted, fluidity was evaluated, and a resin molded body was prepared by transfer molding. At 160 ° C. for 2 hours, further 180 ° C. The flame retardancy of the cured product obtained by curing for 8 hours was evaluated. The results are shown in Table 1. Each characteristic was measured in the following manner. -Spiral flow: based on ASTM F3133-Flame retardance: Evaluation was performed based on UL94. However, the test piece is 12.5 mm wide ⁇ 150 mm long ⁇ 0.8 mm thick. ⁇ Afterflame time: Total afterflame time after 10 times contact with 5 samples
  • Curing agent (H1) Formula (4) below
  • R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent
  • Curing accelerator Triphenylphosphine (manufactured by Hokuko Chemical)
  • Inorganic filler fused silica (trade name MSR4212, manufactured by Tatsumori)
  • Mold release agent Carnauba wax (trade name Carnauba Wax No. 1, manufactured by Celerica Noda)
  • Coupling agent Silane coupling agent (trade name KBM-303, manufactured by Shin-Etsu Chemical)
  • Examples 9 to 12 and Comparative Example 3 Various components are blended in the proportions (parts by weight) shown in Table 2, kneaded with a mixing roll, tableted, prepared by resin molding by transfer molding, and cured by curing at 160 ° C for 2 hours and further at 180 ° C for 8 hours. The physical properties of the cured product were measured. The results are shown in Table 2. In addition, the physical property of hardened
  • the curable composition of the present invention has the same flame retardancy and heat resistance as compared with the composition using the epoxidized product of phenolphthalein alone as the cured product. It has been clarified that excellent properties are exhibited in terms of fluidity during curing and adhesion to metal.
  • the epoxy resin composition of the present invention has a low melt viscosity and excellent fluidity. Moreover, it turns out by using the epoxy resin composition of this invention that it is excellent in the adhesiveness with respect to a metal, and also gives the hardened

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Abstract

Provided is an epoxy resin composition which produces a cured product having a low melt viscosity, excellent fluidity, and also excellent flame-retarding performance, adhesiveness, and heat resistance. The epoxy resin composition comprises an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (1) (1) or an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (2) (2) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (3). (3)

Description

エポキシ樹脂、エポキシ樹脂組成物およびその硬化物Epoxy resin, epoxy resin composition and cured product thereof

　本発明は溶融粘度が低く、流動性に優れ、なおかつ難燃性、密着性、耐熱性に優れた硬化物を与えるエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition having a low melt viscosity, excellent fluidity, and giving a cured product excellent in flame retardancy, adhesion and heat resistance.

　近年、半導体素子の高性能化ならびに使用分野・環境の多様化に伴い、半導体パッケージには小型化、軽量化、薄型化などの形状に関する要求が益々高まっている。また、昨今の環境問題に対する意識の高まりにより、半田の鉛フリー化、パッケージのハロゲンフリー・アンチモンフリー・リンフリー難燃化や、高温や高湿条件下での耐久性に関する要求がされている。 In recent years, with increasing performance of semiconductor elements and diversification of fields of use and environments, there are increasing demands for semiconductor packages regarding shapes such as miniaturization, weight reduction, and thinning. In addition, due to the recent increase in awareness of environmental problems, there are demands for solder lead-free, halogen-free, antimony-free, and phosphorus-free flame retardant packages, and durability under high temperature and high humidity conditions.

日本国特開２００８－１７９７３９号公報Japanese Unexamined Patent Publication No. 2008-179739

　ハロゲンフリー・アンチモンフリー・リンフリー難燃でなおかつ高耐熱の要求特性に応えるエポキシ樹脂組成物としては、これまでにフェノールフタレイン型のエポキシ樹脂が含まれる特許文献１が報告されており、この硬化物はＵＬ９４でＶ－０の難燃性を有しており、優れた耐熱性も示すことが記されている。
　しかしながら、フェノールフタレイン型のエポキシ樹脂は一般的な高耐熱性樹脂と比較すると低粘度であるものの、パッケージのように細密充填化が著しく、高流動性を求められるパッケージ分野においては十分とはいえず、更なる低粘度化が必要である。
　また、パッケージで問題となるクラックの原因一つに、封止樹脂がリードフレームから剥離することにより、この部分に水分が溜まり、これが膨張することによって発生すると考えられている。この解決策として、封止樹脂とリードフレームとの密着性を向上させることによってパッケージクラックを防止することができるものと考えられる。 Patent Document 1 containing a phenolphthalein type epoxy resin has been reported as an epoxy resin composition that meets the required characteristics of halogen-free, antimony-free, phosphorus-free flame retardant and high heat resistance. It is noted that the product has a flame retardancy of V-0 at UL94 and also exhibits excellent heat resistance.
However, although phenolphthalein type epoxy resin has a low viscosity compared with general high heat resistant resin, it is not enough in the packaging field where high fluidity is required, such as packaging, which is remarkably densely packed. However, further reduction in viscosity is necessary.
In addition, it is considered that one of the causes of cracks that cause a problem in the package is that the sealing resin is peeled off from the lead frame, and moisture is accumulated in this portion, which expands. As a solution, it is considered that package cracks can be prevented by improving the adhesion between the sealing resin and the lead frame.

　本発明は上記従来技術における問題点を鑑みてなされたものであり、溶融粘度が低く、流動性に優れ、なおかつ難燃性、密着性、耐熱性に優れた硬化物を与えるエポキシ樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above problems in the prior art, and an epoxy resin composition that provides a cured product having a low melt viscosity, excellent fluidity, and excellent flame retardancy, adhesion, and heat resistance. The purpose is to provide.

　本発明者らは前記課題を解決するために鋭意研究した結果、本発明を完成させるに到った。すなわち本発明は
〔１〕　式（１）

Figure JPOXMLDOC01-appb-C000007
（式中、Ｒ１、ＸおよびＹは独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｋはＲ１の数を表し、１～４の整数を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂および式（２）
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ２、およびＡは独立して存在し、Ｒ２は水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｌはＲ２の数を表し、１～４の整数を表す。Ａは直接結合、もしくはシクロ環を有する炭素数５～１５のアルキリデン基を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂のうち、少なくともいずれか１種のエポキシ樹脂と、
　式（３）
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｒ３及びＲ４はそれぞれ独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｍ及びｎはそれぞれＲ３及びＲ４の数を表し、１～４の整数を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂と、
を含有するエポキシ樹脂組成物、
〔２〕　式（１）
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ１、ＸおよびＹは独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｋはＲ１の数を表し、１～４の整数を表す。）で表されるフェノール化合物および式（２）
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ２、およびＡは独立して存在し、Ｒ２は水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｌはＲ２の数を表し、１～４の整数を表す。Ａは直接結合、もしくはシクロ環を有する炭素数５～１５のアルキリデン基を表す。）で表されるフェノール化合物のうち、少なくとも１種のフェノール化合物と、
式（３）
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ３及びＲ４はそれぞれ独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｍ及びｎはそれぞれＲ３及びＲ４の数を表し、１～４の整数を表す。）で表されるフェノール化合物と、
を含む混合物にエピハロヒドリンを反応させて得られるエポキシ樹脂組成物、
〔３〕　式（１）～（３）で表されるフェノール化合物の混合物のうち、式（１）および（２）から選ばれるフェノール化合物の占める割合が１～３０質量％であるフェノール化合物の混合物にエピハロヒドリンを反応させて得られる上記〔２〕に記載のエポキシ樹脂組成物、
〔４〕　上記〔１〕～〔３〕のいずれか一項に記載のエポキシ樹脂組成物、および硬化剤を含有してなる硬化性樹脂組成物
〔５〕　無機充填剤を含有する上記〔４〕に記載の硬化性樹脂組成物、
〔６〕　上記〔４〕、〔５〕のいずれか一項に記載の硬化性樹脂組成物の硬化物、
〔７〕　上記〔４〕、〔５〕のいずれか一項に記載の硬化性樹脂組成物を用いて成型した半導体封止材料、に関する。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention provides [1] Formula (1)
Figure JPOXMLDOC01-appb-C000007
 (Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 , and represents an integer of 1 to 4.) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (2)
Figure JPOXMLDOC01-appb-C000008
 (Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4. A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring.) At least any one epoxy resin among the epoxy resins obtained, and
Formula (3)
Figure JPOXMLDOC01-appb-C000009
 (Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. And n represents the number of R 3 and R 4 , respectively, and represents an integer of 1 to 4.) An epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by:
An epoxy resin composition containing,
[2] Formula (1)
Figure JPOXMLDOC01-appb-C000010
 (Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 and represents an integer of 1 to 4.) and a phenol compound represented by formula (2)
Figure JPOXMLDOC01-appb-C000011
 (Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4. A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring. One phenolic compound,
Formula (3)
Figure JPOXMLDOC01-appb-C000012
 (Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. And n represents the number of R 3 and R 4 , respectively, and represents an integer of 1 to 4.)
An epoxy resin composition obtained by reacting an epihalohydrin with a mixture containing
[3] A mixture of phenol compounds in which the proportion of the phenol compound selected from formulas (1) and (2) is 1 to 30% by mass in the mixture of phenol compounds represented by formulas (1) to (3) The epoxy resin composition according to the above [2], obtained by reacting an epihalohydrin with
[4] Curable resin composition comprising the epoxy resin composition according to any one of [1] to [3] above and a curing agent [5] The above [4] containing an inorganic filler Curable resin composition according to
[6] A cured product of the curable resin composition according to any one of [4] and [5],
[7] The present invention relates to a semiconductor sealing material molded by using the curable resin composition according to any one of [4] and [5].

　本発明のエポキシ樹脂組成物は難燃性、金属に対する密着性および耐熱性に優れた硬化物を与える樹脂でありながら、なおかつ流動性に優れたエポキシ樹脂組成物である。したがって、本発明のエポキシ樹脂組成物を含む硬化性樹脂組成物は電気・電子材料、成型材料、注型材料、積層材料、塗料、接着剤、レジスト用途、などの広範囲の用途に有用である。 The epoxy resin composition of the present invention is an epoxy resin composition excellent in fluidity while being a resin that gives a cured product excellent in flame retardancy, adhesion to metal and heat resistance. Therefore, the curable resin composition containing the epoxy resin composition of the present invention is useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resist applications, and the like.

　本発明のエポキシ樹脂組成物は、

Figure JPOXMLDOC01-appb-C000013
 （式中、Ｒ１、ＸおよびＹは独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｋはＲ１の数を表し、１～４の整数を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂および式（２）
Figure JPOXMLDOC01-appb-C000014
  （式中、Ｒ２、およびＡは独立して存在し、Ｒ２は水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｌはＲ２の数を表し、１～４の整数を表す。Ａは直接結合、もしくはシクロ環を有する炭素数５～１５のアルキリデン基を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂のうち、少なくともいずれか１種のエポキシ樹脂と、
式（３）
Figure JPOXMLDOC01-appb-C000015
  （式中、Ｒ３及びＲ４はそれぞれ独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｍ及びｎはそれぞれＲ３及びＲ４の数を表し、１～４の整数を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂と、を含有する。 The epoxy resin composition of the present invention is
Figure JPOXMLDOC01-appb-C000013
 (Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 , and represents an integer of 1 to 4.) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (2)
Figure JPOXMLDOC01-appb-C000014
 (Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4. A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring.) At least any one epoxy resin among the epoxy resins obtained, and
Formula (3)
Figure JPOXMLDOC01-appb-C000015
 (Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. And n each represents the number of R 3 and R 4 and represents an integer of 1 to 4.) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by

　式（１）で表されるフェノール化合物としては、各種ビスフェノール類が挙げられる。具体的にはＢＰＦ、ＢＰＡ、ＢＰＥ、Ｍｅｔｈｙｌｅｎｅｂｉｓ－ｐ－ＣＲ、ＴＭ－ＢＰＦ、Ｂｉｓ－Ｃ、ＢｉｓＰ－ＭＩＢＫ、Ｂｉｓ２６Ｘ－Ａ、ＢｉｓＰ－ＡＰ、ＢｉｓＯＰＰ－Ａ、ＵｌｔｒｉｔｅＰ、ＤＨＢＰ、ＢｉｓＯＣ－Ｆ、ＢｉｓＰ－Ｂ、ＢｉｓＰ－ＩＢＴＤ、Ｂｉｓ－ＢＡ、ＢｉｓＰ－ＩＯＴＤ、ＢｉｓＯＩＰＰ－Ａ、ＢｉｓＰ－ＤＥＤ、ＢｉｓＯＳＢＰ－Ａ、ＢｉｓＯＴＢＰ－Ａ、Ｂｉｓ２Ｍ６Ｂ－ＩＢＴＤ、ＢｉｓＯＣＨＰ－Ａ、Ｐｈ－ＣＣ－ＡＰ（いずれも本州化学工業製）などが挙げられる。
　上記式（１）で表されるフェノール化合物としては、上記式（１）中、Ｘ、Ｙはそれぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基であることが好ましく、水素原子または炭素数１～５のアルキル基が特に好ましい。
　さらに、上記式（１）中、Ｒ１は水素原子、炭素数１～３のアルキル基が好ましい。 Various bisphenols are mentioned as a phenolic compound represented by Formula (1). Specifically, BPF, BPA, BPE, Methylenebis-p-CR, TM-BPF, Bis-C, BisP-MIBK, Bis26X-A, BisP-AP, BisOPP-A, UltimateP, DHBP, BisOC-F, BisP- B, BisP-IBTD, Bis-BA, BisP-IOTD, BisOIPP-A, BisP-DED, BisOSBP-A, BisOTBP-A, Bis2M6B-IBTD, BisOCHP-A, Ph-CC-AP (all manufactured by Honshu Chemical Industry) ) And the like.
As the phenol compound represented by the above formula (1), in the above formula (1), X and Y are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is particularly preferable.
Further, in the above formula (1), R 1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

　式（２）で表されるフェノール化合物としては、Ａの箇所が直接結合であるビフェニル骨格のビフェノールや３，３’，５，５’－テトラメチル－４，４’－ビフェノール化合物のほかに、それぞれ相当する環状脂肪族ケトン類とフェノール類とを反応させたフェノール化合物が挙げられる。
　上記式（２）で表されるフェノール化合物としては、上記式（２）中、Ａは直接結合が好ましい。
　さらに、上記式（２）中、Ｒ２は水素原子、炭素数１～３のアルキル基であることが好ましい。
　式（２）で表されるフェノール化合物の具体的な化合物としては下記に示すような化合物が挙げられる。 As the phenolic compound represented by the formula (2), in addition to a biphenyl having a direct bond at the position A and a 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol compound, Examples thereof include phenol compounds obtained by reacting corresponding cycloaliphatic ketones and phenols.
As the phenol compound represented by the above formula (2), A is preferably a direct bond in the above formula (2).
Further, in the above formula (2), R 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Specific examples of the phenol compound represented by the formula (2) include the following compounds.

Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016

　前記フェノール化合物は市販品が入手可能で、例えばＢｉｓＰ－ＣＰ、ＢｉｓＰ－Ｚ、ＢｉｓＰ－ＴＭＣ、ＢｉｓＯＣ－ＴＭＣ、ＢｉｓＰ－ＭＺ、ＢｉｓＰ－３ＭＺ、ＢｉｓＰ－ＩＰＺ、ＢｉｓＣＲ－ＩＰＺ、Ｂｉｓ２６Ｘ－ＩＰＺ、ＢｉｓＰ－ＴＣＤ、ＢｉｓＯＣ－ＣＤＥ、Ｂｉｓ２６Ｘ－ＣＤＥ、ＢｉｓＰ－ＣＨＥＰ、ＢｉｓＰ－ＣＯＣＴ、ＢｉｓＰ－ＣＰｅＤＥ（いずれも本州化学工業製）、ＴＣＤＢＰ（ＭＥＴＲＯＰＯＲＩＴＡＮ ＥＸＩＭＣＨＥＭ ＸＴＤなどが挙げられる。 The phenol compound is commercially available, for example, BisP-CP, BisP-Z, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisP- TCD, BisOC-CDE, Bis26X-CDE, BisP-CHEP, BisP-COCT, BisP-CPeDE (all manufactured by Honshu Chemical Industry Co., Ltd.), TCDBP (METROPOLITAN EXIMCHEM XTD), and the like.

　式（３）で表されるフェノール化合物（フェノールフタレイン類）は、一般にフェノール類とフタル酸類の酸無水物を酸性条件下で反応させることによって合成可能であり、例えばRevistade Chimie(1958),9,151-152「The Synthesis of phenolphtaleinewith chlorosulfonic acid as the condensation agent.」にはクロロスルホン酸を使用したフェノールフタレイン類の合成法が記載されている。
　具体的なＲ３、Ｒ４に適応可能な置換基としては水素原子、炭素数１～１０のアルキル基（メチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソブチル基、シクロブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、シクロペンチル基、ｎ－ヘキシル基、イソヘキシル基、シクロヘキシル基、ｎ－ヘプチル基、シクロヘプチル基、ｎ－オクチル基、シクロオクチル基等の鎖状アルキル基または環状アルキル基、アリル基等）、炭素数１～１０のアリール基（例えばナフトール等の環が縮環したものも含む）、（フェニル基、ナフチル基、トルイル基等）、炭素数１～１０のアルコキシ基（メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、シクロプロポキシ基、ｎ－ブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、イソブトキシ基、シクロブトキシ基、シクロヘキシルオキシ基等の鎖状アルキル基または環状アルキル基、アリルオキシ基等）、のいずれかを表す。具体的な製品としてはフェノールフタレイン、クレゾールフタレイン、ジメトキシフェノールフタレイン等が挙げられる。
　上記式（３）で表されるフェノール化合物としては、上記式（３）中、Ｒ３、Ｒ４はそれぞれ独立して、水素原子、炭素数１～３のアルキル基であることが好ましく、工業的に入手しやすいという観点から、特にフェノールフタレインの使用が好ましい。 The phenolic compound (phenolphthaleins) represented by the formula (3) can be synthesized generally by reacting phenols and acid anhydrides of phthalic acids under acidic conditions. For example, Revistade Chimie (1958), 9,151 -152 “The Synthesis of phenolphtaleine with chlorosulfonic acid as the condensation agent” describes a method for synthesizing phenolphthaleins using chlorosulfonic acid.
Specific substituents applicable to R 3 and R 4 include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group). , Sec-butyl group, tert-butyl group, isobutyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl A chain alkyl group such as a cycloheptyl group, an n-octyl group or a cyclooctyl group, a cyclic alkyl group, an allyl group, or the like, or an aryl group having 1 to 10 carbon atoms (for example, a condensed ring such as naphthol) Including), (phenyl group, naphthyl group, toluyl group, etc.), alkoxy group having 1 to 10 carbon atoms (methoxy group, ethoxy group, n Chain alkyl group such as propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, cyclobutoxy group, cyclohexyloxy group, cyclic alkyl group, allyloxy group, etc. ). Specific products include phenolphthalein, cresolphthalein, dimethoxyphenolphthalein and the like.
As the phenol compound represented by the above formula (3), in the above formula (3), R 3 and R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of easy availability, phenolphthalein is particularly preferable.

　本発明のエポキシ樹脂組成物を得る方法としては、式（１）～（３）の各々のフェノール化合物にエピハロヒドリンをあらかじめ反応させてエポキシ樹脂を得て、各エポキシ樹脂を混合させて得ても構わない。各々のフェノール化合物にエピハロヒドリンを反応させる方法としては公知の方法であれば特に限定なく用いることができるが、具体的には、例えば日本国特開平０５－１５５９７８号公報、日本国特開２００８－１７９７３９号公報に記載の方法を用いることができる。
　しかし、製造上の観点から、式（１）～（３）フェノール化合物の混合物に、エピハロヒドリンを反応させてエポキシ樹脂組成物を得ることが好ましい。 As a method for obtaining the epoxy resin composition of the present invention, an epoxy resin may be obtained by previously reacting each phenol compound of the formulas (1) to (3) with an epihalohydrin, and each epoxy resin may be mixed. Absent. As a method of reacting each of the phenol compounds with epihalohydrin, any known method can be used without particular limitation, and specific examples thereof include, for example, Japanese Patent Application Laid-Open No. 05-155978 and Japanese Patent Application Laid-Open No. 2008-179739. Can be used.
However, from the viewpoint of production, it is preferable to obtain an epoxy resin composition by reacting a mixture of the phenol compounds of formulas (1) to (3) with an epihalohydrin.

　以下、式（１）～（３）フェノール化合物の混合物に、エピハロヒドリンを反応させてエポキシ樹脂組成物を得る方法について説明する。
　式（１）～（３）のフェノール化合物の総量に占める式（１）および（２）から選ばれるフェノール類の量は１～３０質量％、さらに好ましくは５～３０質量％であることが望ましい。フェノールフタレイン類の割合が小さいと耐熱性が劣り、割合が大きいと溶融粘度が大きくなり、金属に対する密着性が劣る。 Hereinafter, a method for obtaining an epoxy resin composition by reacting a mixture of phenol compounds of formulas (1) to (3) with epihalohydrin will be described.
The amount of the phenols selected from the formulas (1) and (2) in the total amount of the phenolic compounds of the formulas (1) to (3) is desirably 1 to 30% by mass, more preferably 5 to 30% by mass. . When the proportion of phenolphthaleins is small, the heat resistance is inferior, and when the proportion is large, the melt viscosity becomes large and the adhesion to metal is inferior.

　本発明のエポキシ樹脂組成物を得る反応において、エピハロヒドリンとしてはエピクロルヒドリン、β―メチルエピクロルヒドリン、エピブロモヒドリン等が使用でき、本発明においては工業的に入手が容易なエピクロルヒドリンが好ましい。エピハロヒドリンの使用量は式（１）～（３）のフェノール化合物の混合物の水酸基１モルあたり通常２～２０モル、好ましくは４～１０モルである。 In the reaction for obtaining the epoxy resin composition of the present invention, epichlorohydrin, β-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, and in the present invention, epichlorohydrin which is easily available industrially is preferable. The amount of epihalohydrin used is usually 2 to 20 mol, preferably 4 to 10 mol, per mol of hydroxyl group in the mixture of phenol compounds of formulas (1) to (3).

　上記反応においてはアルカリ金属水酸化物を使用する。使用できるアルカリ金属水酸化物としては水酸化ナトリウム、水酸化カリウム等が挙げられる。アルカリ金属水酸化物は、固形物であっても、その水溶液を使用してもよい。水溶液を使用する場合は該アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に減圧下、または常圧下連続的に水及びエピハロヒドリンを留出させ、更に分液して水を除去し、エピハロヒドリンを反応系内に連続的に戻す方法でもよい。アルカリ金属水酸化物の使用量は本発明のフェノール化合物の水酸基１モルに対して通常０．８～２．０モルであり、好ましくは１．０～１．８モル、より好ましくは１．０～１．５モルである。 In the above reaction, an alkali metal hydroxide is used. Examples of the alkali metal hydroxide that can be used include sodium hydroxide and potassium hydroxide. The alkali metal hydroxide may be a solid or an aqueous solution thereof. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, followed by liquid separation to remove the water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The amount of the alkali metal hydroxide to be used is usually 0.8 to 2.0 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1 mol of the hydroxyl group of the phenol compound of the present invention. ~ 1.5 moles.

　反応を促進するためにテトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等の４級アンモニウム塩を触媒として添加することは好ましい。４級アンモニウム塩の使用量としては本発明のフェノール化合物の水酸基１モルに対し通常０．１～１５ｇであり、好ましくは０．２～１０ｇである。 In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol compound of the present invention.

　また、メタノール、エタノール、イソプロピルアルコールなどのアルコール類、ジメチルスルホン、ジメチルスルホキシド、テトラヒドロフラン、ジオキサン等の非プロトン性極性溶媒などを添加して反応を行うことが反応進行上好ましい。 In addition, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

　アルコール類を使用する場合、その使用量はエピハロヒドリンの使用量に対し通常２～５０重量％、好ましくは４～２０重量％である。また非プロトン性極性溶媒を用いる場合はエピハロヒドリンの使用量に対し通常５～１００重量％、好ましくは１０～８０重量％である。 When alcohols are used, the amount used is usually 2 to 50% by weight, preferably 4 to 20% by weight, based on the amount of epihalohydrin used. When an aprotic polar solvent is used, it is usually 5 to 100% by weight, preferably 10 to 80% by weight, based on the amount of epihalohydrin used.

　反応温度は通常３０～９０℃であり、好ましくは３５～８０℃である。反応時間は通常０．５～１０時間であり、好ましくは１～８時間である。
　反応終了後、反応物を水洗後、または水洗無しに加熱減圧下でエピハロヒドリンや溶媒等を除去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、回収したエポキシ樹脂をトルエン、メチルイソブチルケトンなどの溶剤に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて反応を行ない、閉環を確実なものにすることも出来る。この場合アルカリ金属水酸化物の使用量は本発明のフェノール化合物の水酸基１モルに対して通常０．０１～０．３モル、好ましくは０．０５～０．２モルである。反応温度は通常５０～１２０℃、反応時間は通常０．５～２時間である。 The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.
After completion of the reaction, the reaction product is washed with water or without washing with water, and the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. Can react to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of the hydroxyl group of the phenol compound of the present invention. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

　反応終了後、生成した塩を濾過、水洗などにより除去し、更に加熱減圧下溶剤を留去することにより本発明のエポキシ樹脂組成物が得られる。 After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin composition of the present invention.

　以上、式（１）～（３）フェノール化合物の混合物に、エピハロヒドリンを反応させてエポキシ樹脂組成物を得る方法について説明したが、上述したように式（１）～（３）の各々のフェノール化合物にエピハロヒドリンをあらかじめ反応させてエポキシ樹脂を得た後、各エポキシ樹脂を混合させてもよい。この場合、式（１）～（３）の各々のフェノール化合物に由来するエポキシ樹脂の総量に占める式（１）および（２）から選ばれるフェノール化合物由来のエポキシ樹脂の量は１～３０質量％、さらに好ましくは５～３０質量％であることが望ましい。式（３）のフェノール化合物由来のエポキシ樹脂の割合が小さいと耐熱性が劣り、割合が大きいと溶融粘度が大きくなり、金属に対する密着性が劣るためである。 The method for obtaining an epoxy resin composition by reacting a mixture of phenol compounds of formulas (1) to (3) with epihalohydrin has been described above. As described above, each phenol compound of formulas (1) to (3) is obtained. Each of the epoxy resins may be mixed after previously reacting with epihalohydrin to obtain an epoxy resin. In this case, the amount of the epoxy resin derived from the phenol compound selected from the formulas (1) and (2) in the total amount of the epoxy resin derived from each phenol compound of the formulas (1) to (3) is 1 to 30% by mass. More preferably, the content is 5 to 30% by mass. When the proportion of the epoxy resin derived from the phenol compound of formula (3) is small, the heat resistance is inferior, and when the proportion is large, the melt viscosity becomes large and the adhesion to the metal is inferior.

　以下、本発明の硬化性樹脂組成物について記載する。
　本発明の硬化性樹脂組成物は本発明のエポキシ樹脂組成物及び硬化剤を必須成分として含有する。本発明の硬化性樹脂組成物において本発明のエポキシ樹脂組成物は単独でまたは他のエポキシ樹脂と併用して使用することが出来る。併用する場合、本発明のエポキシ樹脂組成物が全エポキシ樹脂中に占める割合は３０質量％以上が好ましく、特に４０質量％以上が好ましい。ただし、本発明のエポキシ樹脂組成物を硬化性樹脂組成物の改質剤として使用する場合は、内割りで１～３０質量％の割合で添加する。 Hereinafter, it describes about the curable resin composition of this invention.
The curable resin composition of the present invention contains the epoxy resin composition of the present invention and a curing agent as essential components. In the curable resin composition of the present invention, the epoxy resin composition of the present invention can be used alone or in combination with other epoxy resins. When used together, the proportion of the epoxy resin composition of the present invention in the total epoxy resin is preferably 30% by mass or more, particularly preferably 40% by mass or more. However, when the epoxy resin composition of the present invention is used as a modifier for the curable resin composition, it is added at a ratio of 1 to 30% by mass.

　本発明の硬化性樹脂と併用できる他のエポキシ樹脂としては、ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂などが挙げられる。具体的には、ビスフェノールＡ、ビスフェノールＳ、チオジフェノール、フルオレンビスフェノール、テルペンジフェノール、４，４’－ビフェノール、２，２’‐ビフェノール、３，３’，５，５’－テトラメチル‐[１，１’‐ビフェニル]‐４，４’‐ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス‐（４‐ヒドロキシフェニル）メタン、１，１，２，２‐テトラキス（４‐ヒドロキシフェニル）エタン、フェノール類（フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等）とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ヒドロキシベンズアルデヒド（ｏ‐またはｐ‐）、ヒドロキシアセトフェノン（ｏ‐またはｐ‐）、ジシクロペンタジエン、フルフラール、４，４’‐ビス（クロルメチル）‐１，１’‐ビフェニル、４，４’‐ビス（メトキシメチル）‐１，１’‐ビフェニル、１，４‐ビス（クロロメチル）ベンゼン、１，４‐ビス（メトキシメチル）ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類、アルコール類から誘導されるグリシジルエーテル化物、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエーテル系エポキシ樹脂等の固形または液状エポキシ樹脂が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、２種以上併用してもよい。 Other epoxy resins that can be used in combination with the curable resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde (o- or p-), hydroxyacetophenone (o- or p- , Dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) ) Polycondensates with benzene, 1,4-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, glycidyl etherified products derived from alcohols, alicyclic epoxies Examples thereof include solid or liquid epoxy resins such as resins, glycidylamine epoxy resins, and glycidyl ether epoxy resins, but are not limited thereto. These may be used alone or in combination of two or more.

　本発明の硬化性樹脂組成物が含有する硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノール系化合物、カルボン酸系化合物などが挙げられる。使用できる硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン等のアミン系化合物；ジシアンジアミド、リノレン酸の２量体とエチレンジアミンより合成されるポリアミド樹脂等のアミド系化合物、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等のカルボン酸系化合物、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、テルペンジフェノール、４，４’‐ビフェノール、２，２’‐ビフェノール、３，３’，５，５’‐テトラメチル‐［１，１’‐ビフェニル］‐４，４’‐ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス‐（４‐ヒドロキシフェニル）メタン、１，１，２，２‐テトラキス（４‐ヒドロキシフェニル）エタン、フェノール類（フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等）とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ヒドロキシベンズアルデヒド（ｏ‐またはｐ‐）、ヒドロキシアセトフェノン（ｏ‐またはｐ‐）、ジシクロペンタジエン、フルフラール、４，４’‐ビス（クロロメチル）‐１，１’‐ビフェニル、４，４’‐ビス（メトキシメチル）‐１，１’‐ビフェニル、１，４’‐ビス（クロロメチル）ベンゼン、１，４’‐ビス（メトキシメチル）ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類、テルペンとフェノール類の縮合物等のフェノール系化合物、イミダゾール、トリフルオロボラン‐アミン錯体、グアニジン誘導体などが挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、２種以上を用いてもよい。 Examples of the curing agent contained in the curable resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of curing agents that can be used include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and isophoronediamine; amides such as polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine. Compounds, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Carboxylic acid compounds, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5 5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4 -Hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde (o- or p-), hydroxyacetophenone (o- Or p-), dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4 '-Bis (chloro Phenol compounds such as polycondensates with til) benzene, 1,4′-bis (methoxymethyl) benzene, and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and condensates of terpenes and phenols , Imidazole, trifluoroborane-amine complex, guanidine derivatives and the like, but are not limited thereto. These may be used alone or in combination of two or more.

　本発明の硬化性樹脂組成物において硬化剤の使用量は、エポキシ樹脂成分（本発明のエポキシ樹脂組成物及び他のエポキシ樹脂）のエポキシ基１当量に対して０．７～１．２当量が好ましい。エポキシ基１当量に対して、０．７当量に満たない場合、あるいは１．２当量を超える場合、いずれも硬化が不完全となり良好な硬化物性が得られない恐れがある。 In the curable resin composition of the present invention, the amount of the curing agent used is 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin component (the epoxy resin composition of the present invention and other epoxy resins). preferable. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

　本発明の硬化性樹脂組成物においては、硬化促進剤（硬化触媒）を使用しても差し支えない。使用できる硬化促進剤の具体例としては２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾール等のイミダゾ－ル類、２－（ジメチルアミノメチル）フェノール、１，８－ジアザ‐ビシクロ（５，４，０）ウンデセン－７等の第３級アミン類、トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィントリフェニルボラン等のホスフィン類、オクチル酸スズ等の金属化合物等が挙げられる。硬化促進剤は、エポキシ樹脂成分１００質量部に対して０．０２～５．０質量部が必要に応じ用いられる。 In the curable resin composition of the present invention, a curing accelerator (curing catalyst) may be used. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane, and metal compounds such as tin octylate. The curing accelerator is used in an amount of 0.02 to 5.0 parts by mass based on 100 parts by mass of the epoxy resin component, if necessary.

　さらに本発明の硬化性樹脂組成物には、必要に応じて無機充填剤を添加することができる。無機充填剤としては、結晶シリカ、溶融シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、硫酸バリウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、ジルコニア、フォステライト、ステアタイト、スピネル、チタニア、タルク、クレー、酸化マグネシウム、酸化アルミニウム、酸化ベリリウム、酸化鉄、酸化チタン、窒化アルミニウム、窒化ケイ素、窒化ホウ素、マイカ、ガラス、石英、雲母等の粉体またはこれらを球形化したビーズ等が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、２種以上を用いてもよい。これら無機充填剤の含有量は、本発明の硬化性組成物中において０～９５質量％を占める量が用いられる。本発明においては難燃性、機械性強度から特に５０質量％以上が好ましく、更に好ましくは７０質量％以上である。更に本発明の硬化性組成物には、シランカップリング剤、ステアリン酸、パルミチン酸、ステアリン酸亜鉛、ステアリン酸カルシウム等の離型剤、顔料等の種々の配合剤、各種熱硬化性樹脂を添加することができる。 Furthermore, an inorganic filler can be added to the curable resin composition of the present invention as necessary. Inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, barium sulfate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, clay, Examples include magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, titanium oxide, aluminum nitride, silicon nitride, boron nitride, mica, glass, quartz, and mica powder, or beads made from these. It is not limited. These may be used alone or in combination of two or more. As the content of these inorganic fillers, an amount occupying 0 to 95% by mass in the curable composition of the present invention is used. In the present invention, it is particularly preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of flame retardancy and mechanical strength. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable composition of the present invention. be able to.

　本発明の硬化性樹脂組成物には、成型時の金型との離型を良くするために離型剤を配合することができる。離型剤としては従来公知のものがいずれも使用できるが、例えばカルナバワックス、モンタンワックスなどのエステル系ワックス、ステアリン酸、パルチミン酸などの脂肪酸およびこれらの金属塩、酸化ポリエチレン、非酸化ポリエチレンなどのポリオレフィン系ワックスなどが挙げられる。これらは単独で使用しても２種以上併用しても良い。これら離型剤の配合量は全有機成分に対して０．１質量％～３質量％が好ましい。 In the curable resin composition of the present invention, a release agent can be blended to improve the release from the mold during molding. Any conventionally known release agent can be used as the release agent. For example, ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, polyethylene oxide, non-oxidized polyethylene, etc. Examples include polyolefin wax. These may be used alone or in combination of two or more. The compounding amount of these release agents is preferably 0.1% by mass to 3% by mass with respect to all organic components.

　本発明の硬化性樹脂組成物には、無機充填剤と樹脂成分との接着性を高めるためにカップリング剤を配合することができる。カップリング剤としては従来公知のものがいずれも使用できるが、例えばビニルアルコキシシラン、エポキアルコキシシラン、スチリルアルコキシシラン、メタクリロキシアルコキシシラン、アクリロキシアルコキシシラン、アミノアルコキシシラン、メルカプトアルコキシシラン、イソシアナートアルコキシシランなどの各種アルコキシシラン化合物、アルコキシチタン化合物、アルミニウムキレート類などが挙げられる。これらは単独で使用しても２種以上併用しても良い。カップリング剤の添加方法は、カップリング剤であらかじめ無機充填剤表面を処理した後、樹脂と混練しても良いし、樹脂にカップリング剤を混合してから無機充填剤と混練しても良い。 In the curable resin composition of the present invention, a coupling agent can be blended in order to improve the adhesion between the inorganic filler and the resin component. Any conventionally known coupling agent can be used. For example, vinyl alkoxy silane, epoxy alkoxy silane, styryl alkoxy silane, methacryloxy alkoxy silane, acryloxy alkoxy silane, amino alkoxy silane, mercapto alkoxy silane, isocyanate alkoxy Examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more. The coupling agent may be added by treating the surface of the inorganic filler with the coupling agent in advance and then kneading with the resin, or mixing the coupling agent with the resin and then kneading with the inorganic filler. .

　更に本発明の硬化性樹脂組成物には、必要に応じて公知の添加剤を配合することが出来る。用いうる添加剤の具体例としては、ポリブタジエン及びこの変性物、アクリロニトリル共重合体の変性物、ポリフェニレンエーテル、ポリスチレン、ポリエチレン、ポリイミド、フッ素樹脂、マレイミド系化合物、シアネートエステル系化合物、シリコーンゲル、シリコーンオイル、並びにカーボンブラック、フタロシアニンブルー、フタロシアニングリーン等の着色剤などが挙げられる。 Furthermore, the curable resin composition of the present invention can contain known additives as required. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, and silicone oil. And colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

　本発明の硬化性樹脂組成物は、各成分を均一に分散混合できる従来公知のいかなる手法を用いても製造することができる。例えば各成分を全て粉砕してヘンシェルミキサーなどで混合後、加熱ロールによる溶融混練、ニーダーによる溶融混練、特殊混合機による混合、あるいはこれら各方法の適切な組み合わせを用いることで調製される。また、本発明の半導体装置は、リードフレームなどに搭載された半導体素子を、本発明の硬化性樹脂組成物を用いてトランスファー成型などにより樹脂封止することで製造することができる。 The curable resin composition of the present invention can be produced using any conventionally known technique capable of uniformly dispersing and mixing each component. For example, all the components are pulverized and mixed with a Henschel mixer or the like, then melt kneaded with a heating roll, melt kneaded with a kneader, mixed with a special mixer, or an appropriate combination of these methods. The semiconductor device of the present invention can be manufactured by resin-sealing a semiconductor element mounted on a lead frame or the like by transfer molding or the like using the curable resin composition of the present invention.

　本発明の半導体装置は前記の本発明の硬化性樹脂組成物で封止されたもの等の本発明の硬化性樹脂組成物の硬化物を有する。半導体装置としては、例えばＤＩＰ（デュアルインラインパッケージ）、ＱＦＰ（クワッドフラットパッケージ）、ＢＧＡ（ボールグリッドアレイ）、ＣＳＰ（チップサイズパッケージ）、ＳＯＰ（スモールアウトラインパッケージ）、ＴＳＯＰ（シンスモールアウトラインパッケージ）、ＴＱＦＰ（シンクワッドフラットパッケージ）等が挙げられる。
　また、熱放散性や高速電気特性の問題から、本発明の半導体装置には銅系リードフレームを用いるのが好ましい。銅系のリードフレームとは、銅合金を素材とし、各種メッキ化工を施したリードフレームである。 The semiconductor device of the present invention has a cured product of the curable resin composition of the present invention such as one sealed with the curable resin composition of the present invention. As semiconductor devices, for example, DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package).
Moreover, it is preferable to use a copper-based lead frame for the semiconductor device of the present invention because of problems of heat dissipation and high-speed electrical characteristics. The copper-based lead frame is a lead frame made of a copper alloy and subjected to various plating processes.

　以下、実施例、比較例により本発明を具体的に説明するが、以下において部は特に断わりのない限り重量部である。尚、本発明は以下に限定されるものではない。また、エポキシ当量、ＪＩＳ軟化点、溶融粘度を以下の条件で測定した。
・エポキシ当量　　ＪＩＳ　Ｋ‐７２３６に記載された方法で測定し、単位はｇ／ｅｑである。
・ＪＩＳ軟化点　　ＪＩＳ　Ｋ‐７２３４に記載された方法で測定し、単位は℃である。
・溶融粘度　　１５０℃におけるコーンプレート法による溶融粘度
　　測定機器：コーンプレート（ＩＣＩ）高温粘度計
　　（ＲＥＳＥＡＣＨ　ＥＱＵＩＰＭＥＮＴ（ＬＯＮＤＯＮ）ＬＴＤ.製） EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, a part is a weight part below unless there is particular notice. The present invention is not limited to the following. Moreover, the epoxy equivalent, the JIS softening point, and the melt viscosity were measured under the following conditions.
Epoxy equivalent Measured by the method described in JIS K-7236, and the unit is g / eq.
-JIS softening point It measures by the method described in JIS K-7234, and a unit is (degreeC).
Melt viscosity Melt viscosity by cone plate method at 150 ° C. Measuring instrument: Cone plate (ICI) high temperature viscometer (manufactured by RESEACH EQUIIPMENT (LONDON) LTD.)

実施例１
　撹拌機、還流冷却管、撹拌装置を備えたフラスコに窒素パージを施しながら、フェノールフタレイン１２０部、ビフェノール３０部、エピクロルヒドリン５９７部、ジメチルスルホキシド１２４部、水９部を加え、撹拌下、４５℃にまで昇温し、フレーク状の水酸化ナトリウム４７部を９０分かけて分割添加した後、４５℃のまま１２０分間、６０℃で１２０分、７０℃で６０分間撹拌し、反応を行なった。反応終了後、油層からロータリーエバポレーターを用いて１３０℃で減圧下、過剰のエピクロルヒドリン等を留去した。残留物にメチルイソブチルケトン４２０部を加え、７０℃にまで昇温し溶解した。溶液を水洗し、塩を取り除いた後に、再度７０℃に昇温し、撹拌下で３０重量％の水酸化ナトリウム水溶液１２．２部を加え、９０分間反応を行なった後、洗浄水が中性になるまで水洗を行ない、得られた溶液からロータリーエバポレーターを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することで目的とするエポキシ樹脂組成物（Ｅ１）１９５部を得た。得られたエポキシ樹脂組成物のエポキシ当量は２２２ｇ／ｅｑ、ＪＩＳ軟化点は８７℃、１５０℃におけるＩＣＩ溶融粘度は０．０５Ｐａ・ｓであった。 Example 1
While purging a flask equipped with a stirrer, a reflux condenser, and a stirrer with nitrogen purge, 120 parts of phenolphthalein, 30 parts of biphenol, 597 parts of epichlorohydrin, 124 parts of dimethyl sulfoxide, and 9 parts of water were added and stirred at 45 ° C. The solution was heated to 50 ° C., and 47 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by stirring at 45 ° C. for 120 minutes, 60 ° C. for 120 minutes, and 70 ° C. for 60 minutes. After completion of the reaction, excess epichlorohydrin and the like were distilled off from the oil layer under reduced pressure at 130 ° C. using a rotary evaporator. 420 parts of methyl isobutyl ketone was added to the residue, and the mixture was heated to 70 ° C. and dissolved. The solution was washed with water and the salt was removed, and then the temperature was raised again to 70 ° C., and 12.2 parts of a 30 wt% aqueous sodium hydroxide solution was added with stirring. After reacting for 90 minutes, the wash water was neutral. After washing with water, methyl isobutyl ketone and the like were distilled off from the obtained solution at 180 ° C. under reduced pressure using a rotary evaporator to obtain 195 parts of the desired epoxy resin composition (E1). The epoxy resin composition obtained had an epoxy equivalent of 222 g / eq, a JIS softening point of 87 ° C., and an ICI melt viscosity at 150 ° C. of 0.05 Pa · s.

実施例２
　実施例１とフェノールフタレイン１２０部のところを１４５部、ビフェノール３０部のところをビスフェノールＦ １６部用いる以外は同様の操作を行なうことによりエポキシ樹脂組成物（Ｅ２）１９８部を得た。得られたエポキシ樹脂組成物のエポキシ当量は２３４ｇ／ｅｑ、ＪＩＳ軟化点は５８℃、１５０℃におけるＩＣＩ溶融粘度は０．０７Ｐａ・ｓであった。 Example 2
198 parts of an epoxy resin composition (E2) was obtained in the same manner as in Example 1 except that 145 parts were used for 120 parts of phenolphthalein and 16 parts of bisphenol F were used for 30 parts of biphenol. The epoxy resin composition obtained had an epoxy equivalent of 234 g / eq, a JIS softening point of 58 ° C., and an ICI melt viscosity at 150 ° C. of 0.07 Pa · s.

実施例３
　実施例１とフェノールフタレイン１２０部のところを１６０部、ビフェノール３０部のところをビスフェノールＡ ８．４部用いる以外は同様の操作を行なうことによりエポキシ樹脂組成物（Ｅ３）２０４部を得た。得られたエポキシ樹脂組成物のエポキシ当量は２３３ｇ／ｅｑ、ＪＩＳ軟化点は６５℃、１５０℃におけるＩＣＩ溶融粘度は０．１０Ｐａ・ｓであった。 Example 3
An epoxy resin composition (E3) (204 parts) was obtained in the same manner as in Example 1 except that 160 parts of phenolphthalein and 160 parts of phenolphthalein and 8.4 parts of bisphenol A were used. The obtained epoxy resin composition had an epoxy equivalent of 233 g / eq, a JIS softening point of 65 ° C., and an ICI melt viscosity at 150 ° C. of 0.10 Pa · s.

実施例４
　実施例１とフェノールフタレイン１２０部のところを１３６部、ビフェノール３０部のところをビスフェノールＩ ３４部用いる以外は同様の操作を行なうことによりエポキシ樹脂組成物（Ｅ４）２１４部を得た。得られたエポキシ樹脂組成物のエポキシ当量は２２７ｇ／ｅｑ、ＪＩＳ軟化点は６２℃、１５０℃におけるＩＣＩ溶融粘度は０．０７Ｐａ・ｓであった。 Example 4
An epoxy resin composition (E4) 214 parts was obtained in the same manner as in Example 1 except that 136 parts of phenolphthalein was used and 136 parts of biphenol 30 were used 34 parts of bisphenol I. The epoxy resin composition obtained had an epoxy equivalent of 227 g / eq, a JIS softening point of 62 ° C., and an ICI melt viscosity at 150 ° C. of 0.07 Pa · s.

比較例１
　実施例１とフェノールフタレイン１２０部のところを１７１部用い、ビフェノールを使用しないことを除いては同様の操作を行なうことによりエポキシ樹脂組成物（Ｅ５）２１９部を得た。得られたエポキシ樹脂組成物のエポキシ当量は２４０ｇ／ｅｑ、ＪＩＳ軟化点は６８℃、１５０℃におけるＩＣＩ溶融粘度は０．１１Ｐａ・ｓであった。 Comparative Example 1
Using 171 parts of Example 1 and 120 parts of phenolphthalein, and performing the same operation except not using biphenol, 219 parts of an epoxy resin composition (E5) was obtained. The epoxy equivalent of the obtained epoxy resin composition was 240 g / eq, the JIS softening point was 68 ° C., and the ICI melt viscosity at 150 ° C. was 0.11 Pa · s.

実施例５～８、比較例２ 
　各種成分を表１の割合（重量部）で配合し、ミキシングロールで混練、タブレット化後、流動性の評価をし、トランスファー成型で樹脂成形体を調製し、１６０℃で２時間、更に１８０℃で８時間硬化させて得られた硬化物の難燃性を評価した。結果を表１に示す。
　なお、それぞれの特性は以下の要領で測定した。
・スパイラルフロー：ＡＳＴＭ　Ｆ３１３３に準拠
・難燃性：ＵＬ９４に準拠して評価を行った。ただし、試験片は幅１２．５ｍｍ×長さ１５０ｍｍ×厚さ０．８ｍｍ。
・残炎時間：５個１組のサンプルに１０回接炎したあとの残炎時間の合計 Examples 5 to 8 and Comparative Example 2
Various components were blended in the proportions (parts by weight) shown in Table 1, kneaded with a mixing roll, tableted, fluidity was evaluated, and a resin molded body was prepared by transfer molding. At 160 ° C. for 2 hours, further 180 ° C. The flame retardancy of the cured product obtained by curing for 8 hours was evaluated. The results are shown in Table 1.
Each characteristic was measured in the following manner.
-Spiral flow: based on ASTM F3133-Flame retardance: Evaluation was performed based on UL94. However, the test piece is 12.5 mm wide × 150 mm long × 0.8 mm thick.
・ Afterflame time: Total afterflame time after 10 times contact with 5 samples

Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017

注）硬化剤（Ｈ１）：下記式（４） Note) Curing agent (H1): Formula (4) below

Figure JPOXMLDOC01-appb-C000018
 （式中、複数存在するＲ５はそれぞれ独立して水素原子または炭素数１～４のアルキル基を表す。）で表されるフェノール樹脂（商品名　ＫＡＹＡＨＡＲＤ ＧＰＨ－６５、日本化薬製、水酸基当量１９８ｇ／ｅｑ、ＪＩＳ軟化点６５℃）、
Figure JPOXMLDOC01-appb-C000018
 (Wherein a plurality of R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) (trade name KAYAHARD GPH-65, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent) 198 g / eq, JIS softening point 65 ° C.)

硬化促進剤：トリフェニルホスフィン（北興化学工業製）
無機充填剤：溶融シリカ（商品名　ＭＳＲ４２１２、龍森製）
離型剤：カルナバワックス（商品名　カルナバワックス１号、セラリカ野田製）
カップリング剤：シランカップリング剤（商品名　ＫＢＭ－３０３、信越化学製） Curing accelerator: Triphenylphosphine (manufactured by Hokuko Chemical)
Inorganic filler: fused silica (trade name MSR4212, manufactured by Tatsumori)
Mold release agent: Carnauba wax (trade name Carnauba Wax No. 1, manufactured by Celerica Noda)
Coupling agent: Silane coupling agent (trade name KBM-303, manufactured by Shin-Etsu Chemical)

実施例９～１２および比較例３
　各種成分を表２の割合（重量部）で配合し、ミキシングロールで混練、タブレット化後、トランスファー成形で樹脂成形体を調製し、１６０℃で２時間、更に１８０℃で８時間硬化させて得られた硬化物の物性を測定した。結果を表２に示す。なお、硬化物の物性は以下の要領で測定した。
・ピール強度：ＪＩＳ　Ｋ－６９１１
・ガラス転移温度（ＤＭＡ）：真空理工株式会社製　ＴＭ－７０００により昇温速度　２℃／ｍｉｎ．の条件で測定。 Examples 9 to 12 and Comparative Example 3
Various components are blended in the proportions (parts by weight) shown in Table 2, kneaded with a mixing roll, tableted, prepared by resin molding by transfer molding, and cured by curing at 160 ° C for 2 hours and further at 180 ° C for 8 hours. The physical properties of the cured product were measured. The results are shown in Table 2. In addition, the physical property of hardened | cured material was measured in the following ways.
・ Peel strength: JIS K-6911
Glass transition temperature (DMA): Temperature rise rate 2 ° C./min. Measured under the conditions of

Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019

　表１および２の結果から、本発明の硬化性組成物は、その硬化物がフェノールフタレイン単独のエポキシ化物を使用した組成物と比較して同等の難燃性、耐熱性を保持しつつ、硬化時の流動性や金属との密着性に関しては優れた特性を示すことが明らかとなった。 From the results of Tables 1 and 2, the curable composition of the present invention has the same flame retardancy and heat resistance as compared with the composition using the epoxidized product of phenolphthalein alone as the cured product. It has been clarified that excellent properties are exhibited in terms of fluidity during curing and adhesion to metal.

　本発明のエポキシ樹脂組成物は溶融粘度が小さく、流動性に優れる。また、本発明のエポキシ樹脂組成物を用いることにより、金属に対する密着性に優れ、さらに難燃性および耐熱性にも優れた硬化物を与えることがわかる。したがって、電気・電子材料分野、特に半導体封止に有用である。 The epoxy resin composition of the present invention has a low melt viscosity and excellent fluidity. Moreover, it turns out by using the epoxy resin composition of this invention that it is excellent in the adhesiveness with respect to a metal, and also gives the hardened | cured material excellent also in the flame retardance and heat resistance. Therefore, it is useful in the field of electrical / electronic materials, particularly in semiconductor encapsulation.

　本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
　なお、本出願は、２０１０年５月１４日付で出願された日本特許出願（特願２０１０－１１１５９８）に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on May 14, 2010 (Japanese Patent Application No. 2010-111598), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (7)

　式（１）
Figure JPOXMLDOC01-appb-C000001
  
（式中、Ｒ１、ＸおよびＹは独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｋはＲ１の数を表し、１～４の整数を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂および式（２）
Figure JPOXMLDOC01-appb-C000002
  
（式中、Ｒ２、およびＡは独立して存在し、Ｒ２は水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｌはＲ２の数を表し、１～４の整数を表す。Ａは直接結合、もしくはシクロ環を有する炭素数５～１５のアルキリデン基を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂のうち、少なくともいずれか１種のエポキシ樹脂と、
　式（３）
Figure JPOXMLDOC01-appb-C000003
  
（式中、Ｒ３及びＲ４はそれぞれ独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｍ及びｎはそれぞれＲ３及びＲ４の数を表し、１～４の整数を表す。）で表されるフェノール化合物にエピハロヒドリンを反応させて得られるエポキシ樹脂と、
を含有するエポキシ樹脂組成物。 Formula (1)
Figure JPOXMLDOC01-appb-C000001
(Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 , and represents an integer of 1 to 4.) and an epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by formula (2)
Figure JPOXMLDOC01-appb-C000002
(Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4. A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring.) At least any one epoxy resin among the epoxy resins obtained, and
Formula (3)
Figure JPOXMLDOC01-appb-C000003
(Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. And n represents the number of R 3 and R 4 , respectively, and represents an integer of 1 to 4.) An epoxy resin obtained by reacting an epihalohydrin with a phenol compound represented by:
An epoxy resin composition containing 　式（１）
Figure JPOXMLDOC01-appb-C000004
  
（式中、Ｒ１、ＸおよびＹは独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｋはＲ１の数を表し、１～４の整数を表す。）で表されるフェノール化合物および式（２）
Figure JPOXMLDOC01-appb-C000005
  
（式中、Ｒ２、およびＡは独立して存在し、Ｒ２は水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｌはＲ２の数を表し、１～４の整数を表す。Ａは直接結合、もしくはシクロ環を有する炭素数５～１５のアルキリデン基を表す。）で表されるフェノール化合物のうち、少なくとも１種のフェノール化合物と、
式（３）
Figure JPOXMLDOC01-appb-C000006
  
（式中、Ｒ３及びＲ４はそれぞれ独立して存在し、水素原子、炭素数１～１０のアルキル基もしくはアリール基、水酸基、又は炭素数１～１０のアルコキシ基のいずれかを表す。ｍ及びｎはそれぞれＲ３及びＲ４の数を表し、１～４の整数を表す。）で表されるフェノール化合物と、
を含む混合物にエピハロヒドリンを反応させて得られるエポキシ樹脂組成物。 Formula (1)
Figure JPOXMLDOC01-appb-C000004
(Wherein R 1 , X and Y are independently present and each represents a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.) Represents the number of R 1 and represents an integer of 1 to 4.) and a phenol compound represented by formula (2)
Figure JPOXMLDOC01-appb-C000005
(Wherein R 2 and A are independently present, and R 2 represents any one of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms) L represents the number of R 2 and represents an integer of 1 to 4. A represents a direct bond or an alkylidene group having 5 to 15 carbon atoms having a cyclo ring. One phenolic compound,
Formula (3)
Figure JPOXMLDOC01-appb-C000006
(Wherein R 3 and R 4 are each independently present and represent any of a hydrogen atom, an alkyl or aryl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. And n represents the number of R 3 and R 4 , respectively, and represents an integer of 1 to 4.)
An epoxy resin composition obtained by reacting an epihalohydrin with a mixture containing. 　式（１）～（３）で表されるフェノール化合物の混合物のうち、式（１）および（２）から選ばれるフェノール化合物の占める割合が１～３０質量％であるフェノール化合物の混合物に、エピハロヒドリンを反応させて得られる請求項２に記載のエポキシ樹脂組成物。 In the mixture of phenol compounds represented by the formulas (1) to (3), the proportion of the phenol compound selected from the formulas (1) and (2) is 1 to 30% by mass. The epoxy resin composition according to claim 2 obtained by reacting. 　請求項１～３のいずれか一項に記載のエポキシ樹脂組成物、および硬化剤を含有してなる硬化性樹脂組成物。 A curable resin composition comprising the epoxy resin composition according to any one of claims 1 to 3 and a curing agent. 　無機充填剤を含有する請求項４に記載の硬化性樹脂組成物。 The curable resin composition according to claim 4 containing an inorganic filler. 　請求項４、５のいずれか一項に記載の硬化性樹脂組成物の硬化物。 A cured product of the curable resin composition according to any one of claims 4 and 5. 　請求項４、５のいずれか一項に記載の硬化性樹脂組成物を用いて成型した半導体封止材料。 A semiconductor sealing material molded using the curable resin composition according to claim 4.
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JPWO2015037584A1 (en) * 2013-09-10 2017-03-02 日本化薬株式会社 Epoxy resin mixture, epoxy resin composition, cured product, and semiconductor device
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