WO2012105072A1 - Epoxy resin composition and semiconductor sealing material using same - Google Patents

Epoxy resin composition and semiconductor sealing material using same Download PDF

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Publication number
WO2012105072A1
WO2012105072A1 PCT/JP2011/067640 JP2011067640W WO2012105072A1 WO 2012105072 A1 WO2012105072 A1 WO 2012105072A1 JP 2011067640 W JP2011067640 W JP 2011067640W WO 2012105072 A1 WO2012105072 A1 WO 2012105072A1
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WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
component
mass
total mass
Prior art date
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PCT/JP2011/067640
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French (fr)
Japanese (ja)
Inventor
洋平 細野
洋希 本間
Original Assignee
ナミックス株式会社
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Publication date
Application filed by ナミックス株式会社 filed Critical ナミックス株式会社
Priority to CN201180065777.0A priority Critical patent/CN103328530B/en
Priority to KR1020137019593A priority patent/KR101819264B1/en
Publication of WO2012105072A1 publication Critical patent/WO2012105072A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • 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
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • 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
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • 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 suitable for a semiconductor encapsulant and a semiconductor encapsulant using the same.
  • the semiconductor encapsulant of the present invention can be used for either a semiconductor encapsulant for primary mounting or a semiconductor encapsulant for secondary mounting.
  • Epoxy resin has excellent electrical insulation, mechanical strength, heat resistance, moisture resistance, adhesion, and other material properties, so it can be used as an electrical insulation material for semiconductor sealing materials and electronic parts. It is used.
  • the epoxy resin composition used for such applications usually uses a solvent-free composition and is further used as a semiconductor sealing material. In that case, in order to improve the filling property to the site
  • epoxy resin diluents such as monoglycidyl ethers such as butyl glycidyl ether and phenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and neodecanoic acid glycidyl ester have been used for the purpose of reducing the viscosity of the epoxy resin composition.
  • the viscosity (25 ° C.) of an epoxy resin composition obtained by blending such an epoxy resin diluent is about 350 to 400 cps.
  • the epoxy resin diluent has a certain effect on reducing the viscosity of the epoxy resin composition
  • the cured product of the epoxy resin composition has a significantly reduced heat resistance or moisture resistance.
  • There were problems such as insufficient mechanical strength and electrical characteristics.
  • the glass transition temperature (Tg) of the epoxy resin composition is as low as about 80 to 105 ° C., there are problems such as poor solder ball reinforcement at the time of sealing and cracks in the thermal cycle test.
  • an epoxy resin diluent is mix
  • Patent Document 1 discloses that a specific amount of epoxy compound (specifically, 1,4-cyclohexanedimethanol diglycidyl ether) is used as an epoxy resin diluent (specifically, epoxy (50 to 150 parts by mass with respect to 100 parts by mass of the resin), it has a low viscosity and has excellent heat resistance, voltage resistance, electrical insulation, moisture resistance, mechanical strength and adhesiveness without lowering the curability.
  • An epoxy resin composition comprising: can be provided.
  • the epoxy resin composition described in Patent Document 1 uses an acid anhydride-based curing agent as a curing agent, a low temperature and a short time required for a semiconductor sealing material, particularly a semiconductor sealing material for secondary mounting. Cannot be cured.
  • Semiconductor encapsulants, especially semiconductor encapsulants for secondary mounting are used for mounting on substrates on which other mounting components such as capacitor chip components are mounted. In order to prevent damage, it is required to be cured at a low temperature in a short time, specifically, to be cured at 150 ° C. or less for several minutes.
  • an acid anhydride curing agent is used as a curing agent, Cannot be achieved.
  • an acid anhydride curing agent is used as the curing agent, there is a problem that the pot life (potential time) of the semiconductor sealing material is short.
  • An epoxy resin composition containing 1,4-cyclohexanedimethanol diglycidyl ether as an essential component is also disclosed in Patent Document 2, but this epoxy resin composition contains 1,4-cyclohexanedimethanol diglycidyl ether, Since a mixture of hydrogenated bisphenol A diglycidyl ether is used as an epoxy resin component, the viscosity is high, and when used as a semiconductor encapsulant, the filling property to the site to be sealed is poor.
  • JP-A-8-12741 Japanese Patent Laid-Open No. 6-136092
  • the present invention has a low viscosity and can be cured at a low temperature in a short time, and has excellent heat resistance, voltage resistance, electrical insulation, moisture resistance, mechanical strength, adhesion It is an object of the present invention to provide an epoxy resin composition having a good property, excellent solder ball reinforcement at the time of sealing, and having a long pot life, and a semiconductor sealing material using the same.
  • the present invention comprises (A) an epoxy resin, (B) 1,4-cyclohexanedimethanol diglycidyl ether, (C) an imidazole-based latent curing agent, and (D) a phenol resin.
  • A) an epoxy resin (B) 1,4-cyclohexanedimethanol diglycidyl ether, (C) an imidazole-based latent curing agent, and (D) a phenol resin.
  • the content of the (B) 1,4-cyclohexanedimethanol diglycidyl ether is 0.5 to 80% by mass with respect to the total mass of the (A) epoxy resin and the (B) 1,4-cyclohexanedimethanol diglycidyl ether.
  • the content of the (C) imidazole-based latent curing agent with respect to the total mass of all components of the epoxy resin composition is 5 to 25% by mass, and the content of the (D) with respect to the total mass of all components of the epoxy resin composition (D )
  • the epoxy resin composition of the present invention preferably contains a liquid epoxy resin as the (A) epoxy resin.
  • the epoxy resin composition of the present invention may further contain (E) a borate ester compound.
  • the epoxy resin composition of the present invention may further contain (F) a silica filler.
  • the epoxy resin composition of the present invention may further contain (G) a silane coupling agent.
  • the present invention also provides a semiconductor encapsulant using the epoxy resin composition of the present invention.
  • the epoxy resin composition of the present invention has a low viscosity of 6000 mPa ⁇ s or less at normal temperature (25 ° C.) and good workability.
  • the epoxy resin composition of the present invention is excellent in low-temperature short-time curability and can be cured by heating for several minutes at a temperature of 150 ° C. or lower.
  • the epoxy resin composition of this invention has favorable storage stability in normal temperature (25 degreeC), and its pot life is long.
  • the epoxy resin composition of the present invention is excellent in solder ball reinforcement at the time of sealing, and can suppress generation of cracks in a thermal cycle test. Due to these characteristics, the epoxy resin composition of the present invention is suitable as a semiconductor sealing material of a semiconductor sealing material for primary mounting or secondary mounting.
  • the epoxy resin composition of the present invention contains the following components (A) to (D) as essential components.
  • the epoxy resin (A) is a component that forms the main component of the epoxy resin composition of the present invention.
  • the epoxy resin of component (A) is preferably liquid at normal temperature, but even if it is solid at normal temperature, it should be diluted with another liquid epoxy resin or diluent and used as a liquid. Can do.
  • bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, naphthalene type epoxy resin, ether or poly Examples include ether-based epoxy resins, oxirane ring-containing polybutadiene, and silicone epoxy copolymer resins.
  • the liquid epoxy resin has a bisphenol A type epoxy resin having an average molecular weight of about 400 or less; a branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; Bisphenol F type epoxy resin; phenol novolak type epoxy resin having an average molecular weight of about 570 or less; vinyl (3,4-cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl, adipine Cycloaliphatic epoxies such as bis (3,4-epoxy-6-methylcyclohexylmethyl) acid, 2- (3,4-epoxycyclohexyl) 5,1-spiro (3,4-epoxycyclohexyl) -m-dioxane Resin; 3, 3 ' Biphenyl-type epoxy resins such as 5,5'-t-t
  • An epoxy resin having a silicone skeleton such as 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane can also be used.
  • diepoxide compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diglycidyl ether; trimethylolpropane triglycidyl ether, glycerin triglycidyl ether Examples of the triepoxide compound are also exemplified.
  • a solid or ultra-high viscosity epoxy resin at room temperature examples include high molecular weight bisphenol A type epoxy resin, novolac epoxy resin, tetrabromobisphenol A type epoxy resin, and the like.
  • the These can be used in combination with an epoxy resin and / or a diluent that is liquid at room temperature to adjust fluidity.
  • low-viscosity epoxy resins such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diester It is preferably combined with a diepoxide compound such as glycidyl ether; a triepoxide compound such as trimethylolpropane triglycidyl ether or glycerin triglycidyl ether, or the like.
  • the reactive diluent refers to a compound having one epoxy group and having a relatively low viscosity at room temperature.
  • the epoxy group other polymerizable functional groups, for example, It may have an alkenyl group such as vinyl and allyl; or an unsaturated carboxylic acid residue such as acryloyl and methacryloyl.
  • Such reactive diluents include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, ⁇ -pinene oxide, and the like.
  • Monoepoxide compounds; monoepoxide compounds having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, 1-vinyl-3,4-epoxycyclohexane and the like are exemplified.
  • the epoxy resin as the component (A) may be used alone or in combination of two or more.
  • the epoxy resin itself is preferably liquid at normal temperature.
  • a liquid bisphenol type epoxy resin, a liquid aminophenol type epoxy resin, a silicone-modified epoxy resin, and a naphthalene type epoxy resin are preferable. More preferred are liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, p-aminophenol type liquid epoxy resin, and 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane.
  • DME 1,4-cyclohexanedimethanol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether
  • DME is an epoxy compound prepared by dehydrochlorinating methanol and epichlorohydrin with heating at about 50 to 150 ° C., and is added as an epoxy resin diluent.
  • DME can also be produced by carrying out an epoxidation procedure with hydrogen peroxide using olefin compounds as raw materials without using epichlorohydrin. DME produced by such a procedure has a chlorine concentration as low as 100 ppm or less and is suitable for use as an epoxy resin diluent.
  • DME is highly reactive. Therefore, the viscosity of the epoxy resin composition can be lowered without impairing the cured product properties such as heat resistance, moisture resistance, mechanical strength, and electrical properties.
  • the DME content as the component (B) is 0.5 to 80 with respect to the total mass of the epoxy resin as the component (A) and the DME as the component (B). % By mass. If it is less than 0.5% by mass, the effect of addition of the epoxy resin diluent becomes insufficient, and the viscosity of the epoxy resin composition at room temperature (25 ° C.) cannot be made 6000 mPa ⁇ s or less. On the other hand, if it exceeds 80% by mass, the properties of the cured product are adversely affected, such as a decrease in glass transition temperature (Tg) and adhesion.
  • the DME content as the component (B) is preferably 1 to 70% by mass based on the total mass of the epoxy resin as the component (A) and the DME as the component (B). More preferably, it is 5 mass%.
  • Component (C): Imidazole-based latent curing agent (C) is an epoxy resin curing agent.
  • the reason why the imidazole-based latent curing agent is used as the epoxy resin curing agent is that it is excellent in low-temperature short-time curability and can be cured by heating for several minutes at a temperature of 150 ° C. or lower.
  • the storage stability in normal temperature (25 degreeC) of an epoxy resin composition becomes favorable by using an imidazole system latent hardening
  • the imidazole-based latent curing agent a known imidazole-based latent curing agent can be used.
  • PN23, PN40, and PN-H are examples of PN23, PN40, and PN-H (trade names, all manufactured by Ajinomoto Fine Techno Co., Ltd.). Also, there may be mentioned those obtained by addition reaction with the hydroxyl group of the epoxy adduct of an amine compound, also called microencapsulated imidazole, such as NovaCure HX-3088, NovaCure HX-3941, HX-3742, HX-3722 (trade names, all Asahi Kasei E-Materials). In addition, any 1 type may be used among said imidazole system latent hardening
  • the content of the imidazole-based latent curing agent as the component (C) is 5 to 25% by mass with respect to the total mass of all components of the epoxy resin composition. If it is less than 5% by mass, the low-temperature short-time curability is inferior, and it cannot be cured by heating for several minutes at a temperature of 150 ° C. or lower. On the other hand, if it exceeds 25% by mass, the storage stability of the epoxy resin composition at room temperature (25 ° C.) is lowered, and the pot life is shortened.
  • the content of the imidazole-based latent curing agent as the component (C) is preferably 5.6 to 24.3 mass% with respect to the total mass of all components of the epoxy resin composition.
  • (D) component phenol resin
  • the phenol resin as (D) component is added in order to achieve uniform hardening of an epoxy resin composition.
  • an imidazole-based latent curing agent as a curing agent for the epoxy resin
  • it is excellent in low-temperature short-time curability and can be cured by heating for several minutes at a temperature of 150 ° C. or lower.
  • the curing tends to be non-uniform, resulting in problems such as the appearance of the cured product being deteriorated and the adhesion of the cured product being impaired.
  • a phenol resin it can select widely from what is used also as a hardening
  • Specific examples include allyl acrylic phenol resin (for example, MEH8005 (trade name, manufactured by Meiwa Kasei Kogyo Co., Ltd.)).
  • the content of the phenol resin as the component (D) is 0.5 to 25% by mass with respect to the total mass of all components of the epoxy resin composition. If it is less than 1% by mass, the curing becomes non-uniform during curing at a low temperature for a short time, causing problems such as deterioration of the appearance of the cured product and impaired adhesion of the cured product. On the other hand, if it exceeds 20% by mass, the storage stability of the epoxy resin composition at room temperature (25 ° C.) is lowered, and the pot life is shortened.
  • the content of the phenol resin as the component (D) is preferably 1 to 20.1% by mass relative to the total mass of all components of the epoxy resin composition.
  • the epoxy resin composition of the present invention may contain the components described below as needed in addition to the components (A) to (D).
  • (E) component boric acid ester compound
  • the epoxy resin composition of the present invention improves the storage stability at room temperature (25 ° C.) and prolongs the pot life. You may contain.
  • Examples of the boric acid ester compound of component (E) include 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, Triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl Borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecy
  • the boric acid ester compound is contained as the component (E), it is preferably 0.05 to 5% by mass, and preferably 0.1 to 3% by mass with respect to the total mass of all components of the epoxy resin composition. More preferably, the content is 0.5 to 1.5% by mass.
  • the epoxy resin composition of the present invention comprises a silica filler as the component (F) in order to adjust the viscosity of the resin composition and improve the heat resistance and moisture resistance of the cured product of the resin composition. You may contain.
  • silica filler is contained as component (F), it is preferably 5 to 80% by mass, more preferably 15 to 70% by mass, based on the total mass of all components of the epoxy resin composition, More preferably, it is ⁇ 65 mass%.
  • the shape of the silica filler as the component (F) is not particularly limited, and may be any form such as granular, powder, flakes and the like. Further, the silica filler as the component (F) may be subjected to a surface treatment as necessary. For example, an oxide film may be formed on the particle surface.
  • the average particle diameter of the silica filler as the component (F) (or the average maximum diameter when it is not granular) is not particularly limited, but is 0.01 to 30 ⁇ m, so that the filling property to the site to be sealed is good Therefore, the thickness is preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m.
  • the epoxy resin composition of the present invention may contain a silane coupling agent as the component (G) in order to improve the adhesion of the cured product.
  • a silane coupling agent is contained as the component (G)
  • the content is preferably 0.01 to 10% by mass, and 0.05 to 5% by mass with respect to the total mass of all components of the epoxy resin composition. More preferably, the content is 0.1 to 3% by mass.
  • the epoxy resin composition of the present invention may contain components other than the above (A) to (G) as necessary.
  • Specific examples of such components include fillers, leveling agents, colorants, ion trapping agents, antifoaming agents, antioxidants, flame retardants, and the like.
  • the type and amount of each compounding agent are as usual.
  • the epoxy resin composition of the present invention is prepared by mixing the above components (A) to (D) and optionally the above components (E) to (G) and optional components such as a filler, and stirring them. Prepared. Although mixing and stirring can be performed using a roll mill, of course, it is not limited to this.
  • the epoxy resin as the component (A) is solid, it is preferably liquefied or fluidized and mixed by heating. Even if the components are mixed at the same time, some components may be mixed first, and the remaining components may be mixed later.
  • the epoxy resin composition of the present invention has a low viscosity at room temperature (25 ° C.) of 6000 mPa ⁇ s or less, and has good workability when used in applications such as a semiconductor sealing material.
  • the epoxy resin composition of the present invention has a viscosity at normal temperature (25 ° C.) of preferably 5500 mPa ⁇ s or less, more preferably 4000 mPa ⁇ s or less, and still more preferably 3000 mPa ⁇ s or less.
  • the epoxy resin composition of the present invention has excellent low-temperature and short-time curability, and can be cured by heating at a temperature of 150 ° C. or lower for several minutes (for example, heating at 120 ° C. for 3 minutes).
  • the epoxy resin composition of the present invention preferably has a gel time of 180 seconds or less, more preferably 90 seconds or less, and more preferably 60 seconds or less, as measured by the procedure described in the examples described later. preferable.
  • the epoxy resin composition of the present invention has good storage stability at normal temperature (25 ° C.) and a long pot life.
  • the viscosity after storage for 48 hours in an environment of 25 ° C. and 50% humidity is less than 1.2 times the viscosity before storage, and preferably the viscosity after storage for 168 hours is the viscosity before storage. It is less than 1.2 times.
  • the epoxy resin composition of the present invention is excellent in adhesion, and the peel strength measured by the procedure described in the examples described later is 10 kg or more, preferably 15 kg or more, more preferably 17 kg or more. It is.
  • the epoxy resin composition of the present invention has a glass transition temperature (Tg) of 120 ° C. or higher, it has excellent solder ball reinforcement at the time of sealing, and a thermal cycle test (eg, ⁇ 40 ° C. to 125 ° C. In the durability test of repeating the thermal cycle up to, the occurrence of cracks is suppressed.
  • the epoxy resin composition of the present invention preferably has a glass transition temperature (Tg) of 125 ° C. or higher, more preferably 130 ° C. or higher.
  • the epoxy resin composition of the present invention is suitable as a semiconductor sealing material for primary mounting or secondary mounting.
  • the epoxy resin composition of the present invention is also suitable for adhesives and die bonding agents.
  • Example 1 to 14 Epoxy resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were prepared by kneading the raw materials using a roll mill so that the blending ratios shown in the following table were obtained.
  • surface represents the mass part.
  • surface represents the following, respectively.
  • Epoxy resin bisphenol A type epoxy resin, product name EXA850CRP, manufactured by DIC Corporation
  • DME 1,4-cyclohexanedimethanol diglycidyl ether, product name ZX1658GS, latent curing agent (imidazole-based latent curing agent) manufactured by Nippon Steel Chemical Co., Ltd .: microcapsule type imidazole (imidazole component and bisphenol A type epoxy resin) ),
  • Product name HX3742 phenol resin manufactured by Asahi Kasei E-materials Co., Ltd .: allyl acrylic phenol resin, product name MEH8005, acid anhydride curing agent manufactured by Meiwa Kasei Co., Ltd .: (product name: HN-5500, Hitachi Chemical) Manufactured by Kogyo Corporation)
  • the following evaluation was implemented about the prepared epoxy resin composition.
  • (Appearance of cured product) A test piece in which 10 mg of the sample for evaluation was applied so as to be in contact with the long side surface of the silicon chip (2 ⁇ 20 ⁇ 0.75 mm) adhered on the polyimide film was put in an oven, heated at 120 ° C. for 3 minutes, and epoxy resin The composition was cured. The appearance of the cured product after heating was visually observed. The case where the cured product had no appearance defects or color irregularities such as wrinkles or cocoon skin was marked with ⁇ , and the case where the cured product had appearance defects or color irregularities such as wrinkles was marked with x.
  • Viscosity, pot life Using an EMD viscometer (manufactured by Tokimec Co., Ltd., device name: TV-22), the viscosity (initial viscosity) of an evaluation sample immediately after preparation was measured at a liquid temperature of 25 ° C. and 1 rpm. Thereafter, the viscosity at the time when the sample for evaluation was put in a sealed container and stored for 48 hours in an environment of 25 ° C. and 50% humidity was measured. The case where the viscosity after storage for 48 hours was less than 1.2 times the initial viscosity was marked with ⁇ , and the case where it was 1.2 times or more was marked with x.
  • the viscosity at the time of putting the sample for evaluation in an airtight container and storing it in an environment of 25 ° C. and a humidity of 50% for 168 hours was measured.
  • (Geltime) When 5 mg ⁇ 1 mg of the epoxy resin composition is supplied on a hot plate at 120 ° C., stir in a circle with a stirring bar, and when the stirring bar is lifted and pulled away while being stirred, the thread is pulled Was measured until the time became 5 mm or less.
  • Glass transition temperature (Tg) The glass transition temperature of the cured product that was heat-cured at 120 ° C. for 3 minutes was measured by the TMA method using TM3000 manufactured by Vacuum Riko Co., Ltd.
  • Example 1 (B) component 31.1 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) (C) component (imidazole component) 5.6 mass% (Based on the total mass of all components of the epoxy resin composition) (D) component 5 mass% (Based on the total mass of all components of the epoxy resin composition)
  • Example 2 component 31.2 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) Component (C) (imidazole component) 11.2% by mass (Based on the total mass of all components of the epoxy resin composition) (D) component 5 mass% (Based on the total mass of all components of the epoxy resin composition)
  • Example 8 component 31.2 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) (C) component (imidazole component) 15 mass% (Based on the total mass of all components of the epoxy resin composition) (D) component 9.4 mass% (Based on the total mass of all components of the epoxy resin composition)
  • Example 9 component 31.1 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) (C) component (imidazole component) 15 mass% (Based on the total mass of all components of the epoxy resin composition) (D) Component 14.7 mass% (Based on the total mass of all components of the epoxy resin composition)
  • Example 10 component 31.0 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) (C) component (imidazole component) 15 mass% (Based on the total mass of all components of the epoxy resin composition) (D) component 20.1 mass
  • Comparative Example 1 component 31.1 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) (C) component (imidazole component) 3.0 mass% (Based on the total mass of all components of the epoxy resin composition) (D) component 5 mass% (Based on the total mass of all components of the epoxy resin composition) Comparative Example 2 (B) component 31.2 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) (C) component (imidazole component) 15 mass% (Based on the total mass of all components of the epoxy resin composition) (D) component 0 mass% (Based on the total mass of all components of the epoxy resin composition) Comparative Example 3 (B) component 0 mass% ((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component) (C) component (imidazole component) 15 mass% (Based on the total mass of all components of the epoxy resin composition) (D) component
  • the epoxy resin compositions of Examples 1 to 14 had a good cured product appearance and were uniformly cured. Moreover, the viscosity in 25 degreeC was 6000 mPa * s or less. Moreover, it was confirmed that the gel time is 120 s or less and the low-temperature short-time curability is excellent. Moreover, adhesiveness was favorable and the glass transition temperature (Tg) was 120 degreeC or more. The pot life after storage for 48 hours was also good. In Examples 1-4, 6-9, and 11-14 in which the content of the component (C) is 5.6 to 24.3 mass% and the content of the component (D) is 1 to 20.1 mass% is 168 hours The pot life after storage was also good.
  • Comparative Example 4 which does not contain the component (D), uses an acid anhydride curing agent, and contains a normal amount of microcapsule type imidazole as a curing accelerator, it is cured even after 180 s in gel time evaluation. Thus, it was confirmed that the low temperature short time curability was inferior. The reason for this is considered to be that the curing action by imidazole was delayed by the presence of the acid anhydride curing agent. In addition, since it was confirmed that it was inferior to low temperature short time curability, adhesive evaluation was not actually carried out. Moreover, the pot life after 48 hours storage was inferior. For this reason, pot life evaluation after storage for 168 hours was not performed.

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Abstract

The present invention provides an epoxy resin composition which has a low viscosity, can be cured at a low temperature in a short time, has excellent heat resistance, voltage resistance, electrical insulating properties, moisture resistance, mechanical strength and adhesive properties, has excellent solder ball reinforcing properties during sealing and has a long pot life; and a semiconductor sealing material using this epoxy resin composition. The epoxy resin composition comprises (A) an epoxy resin, (B) 1,4-cyclohexanedimethanol diglycidyl ether, (C) an imidazole-based latent curing agent and (D) a phenolic resin, and is characterized in that the content of the 1,4-cyclohexanedimethanol diglycidyl ether relative to the total mass of the epoxy resin (A) and the 1,4-cyclohexanedimethanol diglycidyl ether (B) is 0.5 to 80 mass %, the content of the imidazole-based latent curing agent (C) relative to the total mass of all the components in the epoxy resin composition is 5 to 25 mass %, and the content of the phenolic resin (D) relative to the total mass of all the components in the epoxy resin composition is 0.5 to 25 mass %.

Description

エポキシ樹脂組成物およびそれを用いた半導体封止材Epoxy resin composition and semiconductor sealing material using the same
　本発明は、半導体封止材に好適なエポキシ樹脂組成物およびそれを用いた半導体封止材に関する。本発明の半導体封止材は、一次実装用の半導体封止材、二次実装用の半導体封止材のいずれにも用いることができる。 The present invention relates to an epoxy resin composition suitable for a semiconductor encapsulant and a semiconductor encapsulant using the same. The semiconductor encapsulant of the present invention can be used for either a semiconductor encapsulant for primary mounting or a semiconductor encapsulant for secondary mounting.
　エポキシ樹脂は、優れた電気絶縁性、機械強度、耐熱性、耐湿性、密着性等の材料特性を有していることから、半導体封止材のような電気、電子部品の電気絶縁用材料として用いられている。 Epoxy resin has excellent electrical insulation, mechanical strength, heat resistance, moisture resistance, adhesion, and other material properties, so it can be used as an electrical insulation material for semiconductor sealing materials and electronic parts. It is used.
　かかる用途に使用されるエポキシ樹脂組成物は、優れた耐電圧性、電気絶縁性を必要とされる結果、通常、無溶剤型の組成物が使用されており、更に半導体封止材として用いられる場合、封止する部位への充填性を向上させるために、低粘度であることが求められる。 As a result of the need for excellent voltage resistance and electrical insulation, the epoxy resin composition used for such applications usually uses a solvent-free composition and is further used as a semiconductor sealing material. In that case, in order to improve the filling property to the site | part to seal, it is calculated | required that it is a low viscosity.
　従来、エポキシ樹脂組成物の粘度を低下させる目的で、ブチルグリシジルエーテル、フェニルグリシジルエーテル等のモノグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ネオデカン酸グリシジルエステル等、各種のエポキシ樹脂希釈剤が提案されており、かかるエポキシ樹脂希釈剤を配合してなるエポキシ樹脂組成物の粘度（２５℃）は３５０～４００ｃｐｓ程度である。 Conventionally, various epoxy resin diluents such as monoglycidyl ethers such as butyl glycidyl ether and phenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and neodecanoic acid glycidyl ester have been used for the purpose of reducing the viscosity of the epoxy resin composition. The viscosity (25 ° C.) of an epoxy resin composition obtained by blending such an epoxy resin diluent is about 350 to 400 cps.
　しかしながら、上記エポキシ樹脂希釈剤は、エポキシ樹脂組成物の粘度を低減することに対しては一定の効果を示すものの、当該エポキシ樹脂組成物の硬化物は、耐熱性が著しく低下したり、耐湿性、機械強度、電気特性等が十分でない等の問題があった。また、エポキシ樹脂組成物のガラス転移温度（Ｔｇ）が８０～１０５℃程度と低いため、封止時のはんだボール補強性が劣り、サーマルサイクル試験においてクラックが発生する等の問題がある。
　また、エポキシ樹脂希釈剤を配合した場合、貯蔵安定性や硬化性の低下などの問題もある。 However, although the epoxy resin diluent has a certain effect on reducing the viscosity of the epoxy resin composition, the cured product of the epoxy resin composition has a significantly reduced heat resistance or moisture resistance. There were problems such as insufficient mechanical strength and electrical characteristics. Further, since the glass transition temperature (Tg) of the epoxy resin composition is as low as about 80 to 105 ° C., there are problems such as poor solder ball reinforcement at the time of sealing and cracks in the thermal cycle test.
Moreover, when an epoxy resin diluent is mix | blended, there also exist problems, such as a storage stability and a fall of sclerosis | hardenability.
　上記した問題を解決するため、特許文献１では、特定のエポキシ系化合物（具体的には、１，４－シクロヘキサンジメタノールジグリシジルエーテル）をエポキシ樹脂希釈剤として所定量（具体的には、エポキシ樹脂１００質量部に対し５０～１５０質量部）適用することにより、低粘度で、硬化性を低下することなく、優れた耐熱性、耐電圧性、電気絶縁性、耐湿性、機械強度、接着性を具備するエポキシ樹脂組成物を提供することができるとしている。 In order to solve the above problems, Patent Document 1 discloses that a specific amount of epoxy compound (specifically, 1,4-cyclohexanedimethanol diglycidyl ether) is used as an epoxy resin diluent (specifically, epoxy (50 to 150 parts by mass with respect to 100 parts by mass of the resin), it has a low viscosity and has excellent heat resistance, voltage resistance, electrical insulation, moisture resistance, mechanical strength and adhesiveness without lowering the curability. An epoxy resin composition comprising: can be provided.
　しかしながら、特許文献１に記載のエポキシ樹脂組成物は、硬化剤として酸無水物系硬化剤を使用するため、半導体封止材、特に二次実装用の半導体封止材において要求される低温短時間での硬化を達成できない。半導体封止材、特に二次実装用の半導体封止材においては、コンデンサーチップ部品などの他の実装部品等が搭載された基板上に実装するのに用いられるため、基板上の構造物の熱ダメージを防止するため、低温短時間で硬化すること、具体的には、１５０℃以下で数分間で硬化することが求められるが、硬化剤として酸無水物系硬化剤を使用した場合、これを達成することができない。
　また、硬化剤として酸無水物系硬化剤を使用するため、半導体封止材のポットライフ（可使時間）が短いという問題がある。 However, since the epoxy resin composition described in Patent Document 1 uses an acid anhydride-based curing agent as a curing agent, a low temperature and a short time required for a semiconductor sealing material, particularly a semiconductor sealing material for secondary mounting. Cannot be cured. Semiconductor encapsulants, especially semiconductor encapsulants for secondary mounting, are used for mounting on substrates on which other mounting components such as capacitor chip components are mounted. In order to prevent damage, it is required to be cured at a low temperature in a short time, specifically, to be cured at 150 ° C. or less for several minutes. When an acid anhydride curing agent is used as a curing agent, Cannot be achieved.
Further, since an acid anhydride curing agent is used as the curing agent, there is a problem that the pot life (potential time) of the semiconductor sealing material is short.
　１，４－シクロヘキサンジメタノールジグリシジルエーテルを必須成分として含むエポキシ樹脂組成物は特許文献２にも開示されているが、このエポキシ樹脂組成物は、１，４－シクロヘキサンジメタノールジグリシジルエーテルと、水素化ビスフェノールＡジグリシジルエーテルと、の混合物をエポキシ樹脂成分とするため、粘度が高く、半導体封止材として用いた場合、封止する部位への充填性に劣る。 An epoxy resin composition containing 1,4-cyclohexanedimethanol diglycidyl ether as an essential component is also disclosed in Patent Document 2, but this epoxy resin composition contains 1,4-cyclohexanedimethanol diglycidyl ether, Since a mixture of hydrogenated bisphenol A diglycidyl ether is used as an epoxy resin component, the viscosity is high, and when used as a semiconductor encapsulant, the filling property to the site to be sealed is poor.
特開平８－１２７４１号公報JP-A-8-12741 特開平６－１３６０９２号公報Japanese Patent Laid-Open No. 6-136092
　本発明は上記した従来技術の問題点を解決するため、低粘度で、低温短時間での硬化が可能であり、優れた耐熱性、耐電圧性、電気絶縁性、耐湿性、機械強度、密着性を具備し、封止時のはんだボール補強性に優れ、かつ、ポットライフが長いエポキシ樹脂組成物、および、それを用いた半導体封止材を提供することを目的とする。 In order to solve the above-mentioned problems of the prior art, the present invention has a low viscosity and can be cured at a low temperature in a short time, and has excellent heat resistance, voltage resistance, electrical insulation, moisture resistance, mechanical strength, adhesion It is an object of the present invention to provide an epoxy resin composition having a good property, excellent solder ball reinforcement at the time of sealing, and having a long pot life, and a semiconductor sealing material using the same.
　上記の目的を達成するため、本発明は、（Ａ）エポキシ樹脂、（Ｂ）１，４－シクロヘキサンジメタノールジグリシジルエーテル、（Ｃ）イミダゾール系潜在性硬化剤、および、（Ｄ）フェノール樹脂よりなり、
　前記（Ａ）エポキシ樹脂および前記（Ｂ）１，４－シクロヘキサンジメタノールジグリシジルエーテルの合計質量に対する前記（Ｂ）１，４－シクロヘキサンジメタノールジグリシジルエーテルの含有量が０．５～８０質量％であり、エポキシ樹脂組成物の全成分の合計質量に対する前記（Ｃ）イミダゾール系潜在性硬化剤の含有量が５～２５質量％であり、エポキシ樹脂組成物の全成分の合計質量に対する前記（Ｄ）フェノール樹脂の含有量が０．５～２５質量％であることを特徴とするエポキシ樹脂組成物を提供する。 In order to achieve the above object, the present invention comprises (A) an epoxy resin, (B) 1,4-cyclohexanedimethanol diglycidyl ether, (C) an imidazole-based latent curing agent, and (D) a phenol resin. Become
The content of the (B) 1,4-cyclohexanedimethanol diglycidyl ether is 0.5 to 80% by mass with respect to the total mass of the (A) epoxy resin and the (B) 1,4-cyclohexanedimethanol diglycidyl ether. The content of the (C) imidazole-based latent curing agent with respect to the total mass of all components of the epoxy resin composition is 5 to 25% by mass, and the content of the (D) with respect to the total mass of all components of the epoxy resin composition (D ) An epoxy resin composition characterized in that the content of phenol resin is 0.5 to 25% by mass.
　本発明のエポキシ樹脂組成物は、前記（Ａ）エポキシ樹脂として、液状エポキシ樹脂を含有することが好ましい。 The epoxy resin composition of the present invention preferably contains a liquid epoxy resin as the (A) epoxy resin.
　本発明のエポキシ樹脂組成物は、さらに（Ｅ）ホウ酸エステル化合物を含有してもよい。 The epoxy resin composition of the present invention may further contain (E) a borate ester compound.
　本発明のエポキシ樹脂組成物は、さらに、（Ｆ）シリカフィラーを含有してもよい。 The epoxy resin composition of the present invention may further contain (F) a silica filler.
　本発明のエポキシ樹脂組成物は、さらに、（Ｇ）シランカップリング剤を含有してもよい。 The epoxy resin composition of the present invention may further contain (G) a silane coupling agent.
　また、本発明は、本発明のエポキシ樹脂組成物を用いた半導体封止材を提供する。 The present invention also provides a semiconductor encapsulant using the epoxy resin composition of the present invention.
　本発明のエポキシ樹脂組成物は、常温（２５℃）での粘度が６０００ｍＰａ・ｓ以下と低く、作業性が良好である。
　本発明のエポキシ樹脂組成物は、低温短時間硬化性に優れており、１５０℃以下の温度で数分間の加熱で硬化することができる。
　また、本発明のエポキシ樹脂組成物は、常温（２５℃）での貯蔵安定性が良好であり、ポットライフが長い。
　また、本発明のエポキシ樹脂組成物は、封止時のはんだボール補強性に優れ、サーマルサイクル試験においてクラック発生を抑制することができる。
　これらの特性により、本発明のエポキシ樹脂組成物は、一次実装用あるいは二次実装用の半導体封止材の半導体封止材として好適である。 The epoxy resin composition of the present invention has a low viscosity of 6000 mPa · s or less at normal temperature (25 ° C.) and good workability.
The epoxy resin composition of the present invention is excellent in low-temperature short-time curability and can be cured by heating for several minutes at a temperature of 150 ° C. or lower.
Moreover, the epoxy resin composition of this invention has favorable storage stability in normal temperature (25 degreeC), and its pot life is long.
Moreover, the epoxy resin composition of the present invention is excellent in solder ball reinforcement at the time of sealing, and can suppress generation of cracks in a thermal cycle test.
Due to these characteristics, the epoxy resin composition of the present invention is suitable as a semiconductor sealing material of a semiconductor sealing material for primary mounting or secondary mounting.
　以下、本発明について詳細に説明する。
　本発明のエポキシ樹脂組成物は、以下に示す（Ａ）～（Ｄ）成分を必須成分として含有する。 Hereinafter, the present invention will be described in detail.
The epoxy resin composition of the present invention contains the following components (A) to (D) as essential components.
（Ａ）成分：エポキシ樹脂
　（Ａ）成分のエポキシ樹脂は、本発明のエポキシ樹脂組成物の主剤をなす成分である。
　（Ａ）成分のエポキシ樹脂は、常温で液状であることが好ましいが、常温で固体のものであっても、他の液状のエポキシ樹脂又は希釈剤により希釈し、液状を示すようにして用いることができる。
　具体的には、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ナフタレン型エポキシ樹脂、エーテル系又はポリエーテル系エポキシ樹脂、オキシラン環含有ポリブタジエン、シリコーンエポキシコポリマー樹脂等が例示される。 Component (A): Epoxy Resin The epoxy resin (A) is a component that forms the main component of the epoxy resin composition of the present invention.
The epoxy resin of component (A) is preferably liquid at normal temperature, but even if it is solid at normal temperature, it should be diluted with another liquid epoxy resin or diluent and used as a liquid. Can do.
Specifically, bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, naphthalene type epoxy resin, ether or poly Examples include ether-based epoxy resins, oxirane ring-containing polybutadiene, and silicone epoxy copolymer resins.
　特に、液状であるエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂の平均分子量が約４００以下のもの；ｐ－グリシジルオキシフェニルジメチルトリスビスフェノールＡジグリシジルエーテルのような分岐状多官能ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；フェノールノボラック型エポキシ樹脂の平均分子量が約５７０以下のもの；ビニル（３，４－シクロヘキセン）ジオキシド、３，４－エポキシシクロヘキシルカルボン酸（３，４－エポキシシクロヘキシル）メチル、アジピン酸ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）、２－（３，４－エポキシシクロヘキシル）５，１－スピロ（３，４－エポキシシクロヘキシル）－ｍ－ジオキサンのような脂環式エポキシ樹脂；３，３´，５，５´－テトラメチル－４，４´－ジグリシジルオキシビフェニルのようなビフェニル型エポキシ樹脂；ヘキサヒドロフタル酸ジグリシジル、３－メチルヘキサヒドロフタル酸ジグリシジル、ヘキサヒドロテレフタル酸ジグリシジルのようなグリシジルエステル型エポキシ樹脂；ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジル－ｐ－アミノフェノール、テトラグリシジル－ｍ－キシリレンジアミン、テトラグリシジルビス（アミノメチル）シクロヘキサンのようなグリシジルアミン型エポキシ樹脂；ならびに１，３－ジグリシジル－５－メチル－５－エチルヒダントインのようなヒダントイン型エポキシ樹脂；ナフタレン環含有エポキシ樹脂が例示される。また、１，３－ビス（３－グリシドキシプロピル）－１，１，３，３－テトラメチルジシロキサンのようなシリコーン骨格をもつエポキシ樹脂も使用することができる。さらに、（ポリ）エチレングリコールジグリシジルエーテル、（ポリ）プロピレングリコールジグルシジルエーテル、ブタンジオールグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテルのようなジエポキシド化合物；トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテルのようなトリエポキシド化合物等も例示される。 In particular, the liquid epoxy resin has a bisphenol A type epoxy resin having an average molecular weight of about 400 or less; a branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; Bisphenol F type epoxy resin; phenol novolak type epoxy resin having an average molecular weight of about 570 or less; vinyl (3,4-cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl, adipine Cycloaliphatic epoxies such as bis (3,4-epoxy-6-methylcyclohexylmethyl) acid, 2- (3,4-epoxycyclohexyl) 5,1-spiro (3,4-epoxycyclohexyl) -m-dioxane Resin; 3, 3 ' Biphenyl-type epoxy resins such as 5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; glycidyl esters such as diglycidyl hexahydrophthalate, diglycidyl 3-methylhexahydrophthalate, diglycidyl hexahydroterephthalate Type epoxy resins; glycidylamine type epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, tetraglycidylbis (aminomethyl) cyclohexane; and 1,3 -Hydantoin type epoxy resins such as diglycidyl-5-methyl-5-ethylhydantoin; naphthalene ring-containing epoxy resins are exemplified. An epoxy resin having a silicone skeleton such as 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane can also be used. Furthermore, diepoxide compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diglycidyl ether; trimethylolpropane triglycidyl ether, glycerin triglycidyl ether Examples of the triepoxide compound are also exemplified.
　常温で固体ないし超高粘性のエポキシ樹脂を併用することも可能であり、そのようなエポキシ樹脂として、高分子量のビスフェノールＡ型エポキシ樹脂、ノボラックエポキシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂等が例示される。これらは、常温で液体であるエポキシ樹脂及び／又は希釈剤と組み合わせて、流動性を調節して使用することができる。 It is also possible to use a solid or ultra-high viscosity epoxy resin at room temperature, and examples of such an epoxy resin include high molecular weight bisphenol A type epoxy resin, novolac epoxy resin, tetrabromobisphenol A type epoxy resin, and the like. The These can be used in combination with an epoxy resin and / or a diluent that is liquid at room temperature to adjust fluidity.
　常温で固体ないし超高粘性であるエポキシ樹脂を用いる場合、低粘度のエポキシ樹脂、例えば、（ポリ）エチレングリコールジグリシジルエーテル、（ポリ）プロピレングリコールジグルシジルエーテル、ブタンジオールグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテルのようなジエポキシド化合物；トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテルのようなトリエポキシド化合物等と組み合わせることが好ましい。 When using an epoxy resin that is solid or ultra-highly viscous at room temperature, low-viscosity epoxy resins such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diester It is preferably combined with a diepoxide compound such as glycidyl ether; a triepoxide compound such as trimethylolpropane triglycidyl ether or glycerin triglycidyl ether, or the like.
　希釈剤を用いる場合、非反応性希釈剤及び反応性希釈剤のいずれをも使用することができるが、反応性希釈剤が好ましい。本明細書において、反応性希釈剤は、１個のエポキシ基を有する、常温で比較的低粘度の化合物をいうこととし、目的に応じて、エポキシ基以外に、他の重合性官能基、たとえばビニル、アリル等のアルケニル基；又はアクリロイル、メタクリロイル等の不飽和カルボン酸残基を有していてもよい。このような反応性希釈剤としては、ｎ－ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、クレジルグリシジルエーテル、ｐ－ｓ－ブチルフェニルグリシジルエーテル、スチレンオキシド、α－ピネンオキシドのようなモノエポキシド化合物；アリルグリシジルエーテル、メタクリル酸グリシジル、１－ビニル－３，４－エポキシシクロヘキサンのような他の官能基を有するモノエポキシド化合物等が例示される。 When a diluent is used, either a non-reactive diluent or a reactive diluent can be used, but a reactive diluent is preferred. In the present specification, the reactive diluent refers to a compound having one epoxy group and having a relatively low viscosity at room temperature. In addition to the epoxy group, other polymerizable functional groups, for example, It may have an alkenyl group such as vinyl and allyl; or an unsaturated carboxylic acid residue such as acryloyl and methacryloyl. Such reactive diluents include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, α-pinene oxide, and the like. Monoepoxide compounds; monoepoxide compounds having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, 1-vinyl-3,4-epoxycyclohexane and the like are exemplified.
　（Ａ）成分としてのエポキシ樹脂は、単独でも、２種以上併用してもよい。エポキシ樹脂自体が、常温で液状であることが好ましい。中でも好ましくは、液状ビスフェノール型エポキシ樹脂、液状アミノフェノール型エポキシ樹脂、シリコーン変性エポキシ樹脂、ナフタレン型エポキシ樹脂である。さらに好ましくは液状ビスフェノールＡ型エポキシ樹脂、液状ビスフェノールＦ型エポキシ樹脂、ｐ－アミノフェノール型液状エポキシ樹脂、１，３－ビス（３－グリシドキシプロピル）テトラメチルジシロキサンである。 The epoxy resin as the component (A) may be used alone or in combination of two or more. The epoxy resin itself is preferably liquid at normal temperature. Among these, a liquid bisphenol type epoxy resin, a liquid aminophenol type epoxy resin, a silicone-modified epoxy resin, and a naphthalene type epoxy resin are preferable. More preferred are liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, p-aminophenol type liquid epoxy resin, and 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane.
（Ｂ）成分：１，４－シクロヘキサンジメタノールジグリシジルエーテル
　（Ｂ）成分としての１，４－シクロヘキサンジメタノールジグリシジルエーテル（以下、「ＤＭＥ」と略記する。）は、１，４－シクロヘキサンジメタノールとエピクロルヒドリンとを５０～１５０℃程度の加熱下に脱塩酸して調製されるエポキシ系化合物であり、エポキシ樹脂希釈剤として添加される。
　また、エピクロルヒドリンを用いずに、オレフィン化合物を原材料として、過酸化水素によるエポキシ化の手順を実施することによってもＤＭＥを製造することができる。このような手順で製造されるＤＭＥは塩素濃度が１００ｐｐｍ以下と低く、エポキシ樹脂希釈剤として用いるのに好適である。
　ＤＭＥは、ブチルグリシジルエーテル、フェニルグリシジルエーテル等のモノグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ネオデカン酸グリシジルエステルといった従来のエポキシ樹脂希釈剤とは違い、反応性が高いため、添加による反応性低下を抑制できるため、耐熱性、耐湿性、機械強度、電気特性といった硬化物特性を損なうことなしに、エポキシ樹脂組成物の粘度を下げることができる。 Component (B): 1,4-cyclohexanedimethanol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether (hereinafter abbreviated as “DME”) as component (B) It is an epoxy compound prepared by dehydrochlorinating methanol and epichlorohydrin with heating at about 50 to 150 ° C., and is added as an epoxy resin diluent.
Further, DME can also be produced by carrying out an epoxidation procedure with hydrogen peroxide using olefin compounds as raw materials without using epichlorohydrin. DME produced by such a procedure has a chlorine concentration as low as 100 ppm or less and is suitable for use as an epoxy resin diluent.
Unlike conventional epoxy resin diluents such as monoglycidyl ethers such as butyl glycidyl ether and phenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and neodecanoic acid glycidyl ester, DME is highly reactive. Therefore, the viscosity of the epoxy resin composition can be lowered without impairing the cured product properties such as heat resistance, moisture resistance, mechanical strength, and electrical properties.
　本発明のエポキシ樹脂組成物において、（Ｂ）成分としてのＤＭＥ含有量は、（Ａ）成分のエポキシ樹脂と、（Ｂ）成分としてのＤＭＥと、の合計質量に対して、０．５～８０質量％である。０．５質量％未満だと、エポキシ樹脂希釈剤の添加による効果が不十分となり、エポキシ樹脂組成物の常温（２５℃）での粘度を６０００ｍＰａ・ｓ以下とすることができない。
　一方、８０質量％超だと、ガラス転移温度（Ｔｇ）や密着性の低下が起こる等、硬化物特性に悪影響が生じる。
（Ｂ）成分としてのＤＭＥ含有量は、（Ａ）成分のエポキシ樹脂と、（Ｂ）成分としてのＤＭＥと、の合計質量に対して、１～７０質量％であることが好ましく、５～６２．５質量％であることがより好ましい。 In the epoxy resin composition of the present invention, the DME content as the component (B) is 0.5 to 80 with respect to the total mass of the epoxy resin as the component (A) and the DME as the component (B). % By mass. If it is less than 0.5% by mass, the effect of addition of the epoxy resin diluent becomes insufficient, and the viscosity of the epoxy resin composition at room temperature (25 ° C.) cannot be made 6000 mPa · s or less.
On the other hand, if it exceeds 80% by mass, the properties of the cured product are adversely affected, such as a decrease in glass transition temperature (Tg) and adhesion.
The DME content as the component (B) is preferably 1 to 70% by mass based on the total mass of the epoxy resin as the component (A) and the DME as the component (B). More preferably, it is 5 mass%.
（Ｃ）成分：イミダゾール系潜在性硬化剤
　（Ｃ）成分のイミダゾール系潜在性硬化剤はエポキシ樹脂の硬化剤である。エポキシ樹脂の硬化剤として、イミダゾール系潜在性硬化剤を用いるのは、低温短時間硬化性に優れており、１５０℃以下の温度で数分間の加熱で硬化することができるからである。
　また、イミダゾール系潜在性硬化剤を用いることにより、エポキシ樹脂組成物の常温（２５℃）での貯蔵安定性が良好となり、ポットライフを長くすることができる。
　イミダゾール系潜在性硬化剤としては、公知のイミダゾール系潜在性硬化剤を用いることができる。具体例としては、ＰＮ２３、ＰＮ４０、ＰＮ－Ｈ（商品名、いずれも味の素ファインテクノ社製）があげられる。また、マイクロカプセル化イミダゾールとも呼ばれる、アミン化合物のエポキシアダクトの水酸基に付加反応させたものが挙げられ、例えばノバキュアＨＸ－３０８８、ノバキュアＨＸ－３９４１、ＨＸ－３７４２、ＨＸ－３７２２（商品名、いずれも旭化成イーマテリアルズ社製）等として入手可能である。
　なお、上記のイミダゾール系潜在性硬化剤のうち、いずれか１種を使用してもよく、２種以上を併用してもよい。 Component (C): Imidazole-based latent curing agent (C) The imidazole-based latent curing agent of component (C) is an epoxy resin curing agent. The reason why the imidazole-based latent curing agent is used as the epoxy resin curing agent is that it is excellent in low-temperature short-time curability and can be cured by heating for several minutes at a temperature of 150 ° C. or lower.
Moreover, the storage stability in normal temperature (25 degreeC) of an epoxy resin composition becomes favorable by using an imidazole system latent hardening | curing agent, and a pot life can be lengthened.
As the imidazole-based latent curing agent, a known imidazole-based latent curing agent can be used. Specific examples include PN23, PN40, and PN-H (trade names, all manufactured by Ajinomoto Fine Techno Co., Ltd.). Also, there may be mentioned those obtained by addition reaction with the hydroxyl group of the epoxy adduct of an amine compound, also called microencapsulated imidazole, such as NovaCure HX-3088, NovaCure HX-3941, HX-3742, HX-3722 (trade names, all Asahi Kasei E-Materials).
In addition, any 1 type may be used among said imidazole system latent hardening | curing agents, and 2 or more types may be used together.
　本発明のエポキシ樹脂組成物において、（Ｃ）成分としてのイミダゾール系潜在性硬化剤の含有量は、エポキシ樹脂組成物の全成分の合計質量に対して、５～２５質量％である。
　５質量％未満だと、低温短時間硬化性に劣り、１５０℃以下の温度で数分間の加熱で硬化することができない。一方、２５質量％超だと、エポキシ樹脂組成物の常温（２５℃）での貯蔵安定性が低下し、ポットライフが短くなる。
　（Ｃ）成分としてのイミダゾール系潜在性硬化剤含有量は、エポキシ樹脂組成物の全成分の合計質量に対して、５．６～２４．３質量％であることが好ましい。 In the epoxy resin composition of the present invention, the content of the imidazole-based latent curing agent as the component (C) is 5 to 25% by mass with respect to the total mass of all components of the epoxy resin composition.
If it is less than 5% by mass, the low-temperature short-time curability is inferior, and it cannot be cured by heating for several minutes at a temperature of 150 ° C. or lower. On the other hand, if it exceeds 25% by mass, the storage stability of the epoxy resin composition at room temperature (25 ° C.) is lowered, and the pot life is shortened.
The content of the imidazole-based latent curing agent as the component (C) is preferably 5.6 to 24.3 mass% with respect to the total mass of all components of the epoxy resin composition.
（Ｄ）成分：フェノール樹脂
　（Ｄ）成分としてのフェノール樹脂は、エポキシ樹脂組成物の均一な硬化を達成するために添加される。本発明のエポキシ樹脂組成物では、エポキシ樹脂の硬化剤として、イミダゾール系潜在性硬化剤を用いることで、低温短時間硬化性に優れ、１５０℃以下の温度で数分間の加熱で硬化することができるが、低温短時間での硬化時において、硬化が不均一となりやすく、硬化物の外観が悪化する、硬化物の密着性が損なわれる等の問題が生じる。
　フェノール樹脂としては、エポキシ樹脂の硬化剤としても用いられるものから幅広く選択することができる。具体的には、アリルアクリルフェノール樹脂（たとえば、ＭＥＨ８００５（商品名、明和化成工業社製））等が挙げられる。 (D) component: phenol resin The phenol resin as (D) component is added in order to achieve uniform hardening of an epoxy resin composition. In the epoxy resin composition of the present invention, by using an imidazole-based latent curing agent as a curing agent for the epoxy resin, it is excellent in low-temperature short-time curability and can be cured by heating for several minutes at a temperature of 150 ° C. or lower. However, at the time of curing at a low temperature in a short time, the curing tends to be non-uniform, resulting in problems such as the appearance of the cured product being deteriorated and the adhesion of the cured product being impaired.
As a phenol resin, it can select widely from what is used also as a hardening | curing agent of an epoxy resin. Specific examples include allyl acrylic phenol resin (for example, MEH8005 (trade name, manufactured by Meiwa Kasei Kogyo Co., Ltd.)).
　本発明のエポキシ樹脂組成物において、（Ｄ）成分としてのフェノール樹脂の含有量は、エポキシ樹脂組成物の全成分の合計質量に対して、０．５～２５質量％である。
　１質量％未満だと、低温短時間硬化時において、硬化が不均一となり、硬化物の外観が悪化する、硬化物の密着性が損なわれる等の問題が生じる。
　一方、２０質量％超だと、エポキシ樹脂組成物の常温（２５℃）での貯蔵安定性が低下し、ポットライフが短くなる。
　（Ｄ）成分としてのフェノール樹脂含有量は、エポキシ樹脂組成物の全成分の合計質量に対して、１～２０．１質量％であることが好ましい。 In the epoxy resin composition of the present invention, the content of the phenol resin as the component (D) is 0.5 to 25% by mass with respect to the total mass of all components of the epoxy resin composition.
If it is less than 1% by mass, the curing becomes non-uniform during curing at a low temperature for a short time, causing problems such as deterioration of the appearance of the cured product and impaired adhesion of the cured product.
On the other hand, if it exceeds 20% by mass, the storage stability of the epoxy resin composition at room temperature (25 ° C.) is lowered, and the pot life is shortened.
The content of the phenol resin as the component (D) is preferably 1 to 20.1% by mass relative to the total mass of all components of the epoxy resin composition.
　本発明のエポキシ樹脂組成物は、上記（Ａ）～（Ｄ）成分以外に、以下に述べる成分を必要に応じて含有してもよい。 The epoxy resin composition of the present invention may contain the components described below as needed in addition to the components (A) to (D).
（Ｅ）成分：ホウ酸エステル化合物
　本発明のエポキシ樹脂組成物は、常温（２５℃）での貯蔵安定性を向上させ、ポットライフを長くするために、（Ｅ）成分としてホウ酸エステル化合物を含有してもよい。
　（Ｅ）成分のホウ酸エステル化合物としては、例えば、２，２’－オキシビス（５，５’－ジメチル－１，３，２－オキサボリナン）、トリメチルボレート、トリエチルボレート、トリ－ｎ－プロピルボレート、トリイソプロピルボレート、トリ－ｎ－ブチルボレート、トリペンチルボレート、トリアリルボレート、トリヘキシルボレート、トリシクロヘキシルボレート、トリオクチルボレート、トリノニルボレート、トリデシルボレート、トリドデシルボレート、トリヘキサデシルボレート、トリオクタデシルボレート、トリス（２－エチルヘキシロキシ）ボラン、ビス（１，４，７，１０－テトラオキサウンデシル）（１，４，７，１０，１３－ペンタオキサテトラデシル）（１，４，７－トリオキサウンデシル）ボラン、トリベンジルボレート、トリフェニルボレート、トリ－ｏ－トリルボレート、トリ－ｍ－トリルボレート、トリエタノールアミンボレートを用いることができる。
　（Ｅ）成分としてホウ酸エステル化合物を含有させる場合、エポキシ樹脂組成物の全成分の合計質量に対して、０．０５～５質量％であることが好ましく、０．１～３質量％であることがより好ましく、０．５～１．５質量％であることがさらに好ましい。 (E) component: boric acid ester compound The epoxy resin composition of the present invention improves the storage stability at room temperature (25 ° C.) and prolongs the pot life. You may contain.
Examples of the boric acid ester compound of component (E) include 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, Triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl Borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7- Trioxaundecyl) borane, tribenzylbo Over bets it can be used triphenyl borate, tri -o- Toriruboreto, tri -m- Toriruboreto, triethanolamine borate.
When the boric acid ester compound is contained as the component (E), it is preferably 0.05 to 5% by mass, and preferably 0.1 to 3% by mass with respect to the total mass of all components of the epoxy resin composition. More preferably, the content is 0.5 to 1.5% by mass.
（Ｆ）成分：シリカフィラー
　本発明のエポキシ樹脂組成物は、樹脂組成物の粘度調節や、樹脂組成物の硬化物の耐熱性、耐湿性を向上させるために、（Ｆ）成分としてシリカフィラーを含有してもよい。
　（Ｆ）成分としてシリカフィラーを含有させる場合、エポキシ樹脂組成物の全成分の合計質量に対して、５～８０質量％であることが好ましく、１５～７０質量％であることがより好ましく、２０～６５質量％であることがさらに好ましい。 (F) Component: Silica Filler The epoxy resin composition of the present invention comprises a silica filler as the component (F) in order to adjust the viscosity of the resin composition and improve the heat resistance and moisture resistance of the cured product of the resin composition. You may contain.
When silica filler is contained as component (F), it is preferably 5 to 80% by mass, more preferably 15 to 70% by mass, based on the total mass of all components of the epoxy resin composition, More preferably, it is ˜65 mass%.
　（Ｆ）成分としてのシリカフィラーの形状は、特に限定されず、粒状、粉末状、りん片等のいずれの形態であってもよい。
　また、（Ｆ）成分としてのシリカフィラーは、必要に応じて、表面処理を施されたものであってもよい。例えば、粒子表面に酸化皮膜を形成させたものであってもよい。 The shape of the silica filler as the component (F) is not particularly limited, and may be any form such as granular, powder, flakes and the like.
Further, the silica filler as the component (F) may be subjected to a surface treatment as necessary. For example, an oxide film may be formed on the particle surface.
　（Ｆ）成分としてのシリカフィラーの平均粒径（粒状でない場合は、その平均最大径）は、特に限定されないが、０．０１～３０μｍであることが、封止する部位への充填性が良好となることから好ましく、０．０５～２０μｍであることがより好ましく、０．１～１０μｍであることがさらに好ましい。 The average particle diameter of the silica filler as the component (F) (or the average maximum diameter when it is not granular) is not particularly limited, but is 0.01 to 30 μm, so that the filling property to the site to be sealed is good Therefore, the thickness is preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm.
（Ｇ）成分：シランカップリング剤
　本発明のエポキシ樹脂組成物は、硬化物の密着性を向上させるために、（Ｇ）成分としてシランカップリング剤を含有してもよい。
　（Ｇ）成分としてシランカップリング剤を含有させる場合、エポキシ樹脂組成物の全成分の合計質量に対して、０．０１～１０質量％であることが好ましく、０．０５～５質量％であることがより好ましく、０．１～３質量％であることがさらに好ましい。 (G) Component: Silane Coupling Agent The epoxy resin composition of the present invention may contain a silane coupling agent as the component (G) in order to improve the adhesion of the cured product.
When a silane coupling agent is contained as the component (G), the content is preferably 0.01 to 10% by mass, and 0.05 to 5% by mass with respect to the total mass of all components of the epoxy resin composition. More preferably, the content is 0.1 to 3% by mass.
　本発明のエポキシ樹脂組成物は、上記（Ａ）～（Ｇ）以外の成分を必要に応じて含有してもよい。このような成分の具体例としては、充填剤、レベリング剤、着色剤、イオントラップ剤、消泡剤、酸化防止剤、難燃剤などを配合することができる。各配合剤の種類、配合量は常法通りである。 The epoxy resin composition of the present invention may contain components other than the above (A) to (G) as necessary. Specific examples of such components include fillers, leveling agents, colorants, ion trapping agents, antifoaming agents, antioxidants, flame retardants, and the like. The type and amount of each compounding agent are as usual.
（エポキシ樹脂組成物の調製）
　本発明のエポキシ樹脂組成物は、上記の（Ａ）～（Ｄ）成分、ならびに、場合により、上記（Ｅ）～（Ｇ）成分、および、充填剤等の任意成分を混合し、攪拌して調製される。混合攪拌は、ロールミルを用いて行うことができるが、勿論、これに限定されない。（Ａ）成分としてのエポキシ樹脂が固形の場合には、加熱などにより液状化ないし流動化し混合することが好ましい。
　各成分を同時に混合しても、一部成分を先に混合し、残り成分を後から混合するなど、適宜変更しても差支えない。 (Preparation of epoxy resin composition)
The epoxy resin composition of the present invention is prepared by mixing the above components (A) to (D) and optionally the above components (E) to (G) and optional components such as a filler, and stirring them. Prepared. Although mixing and stirring can be performed using a roll mill, of course, it is not limited to this. When the epoxy resin as the component (A) is solid, it is preferably liquefied or fluidized and mixed by heating.
Even if the components are mixed at the same time, some components may be mixed first, and the remaining components may be mixed later.
　以下、本発明のエポキシ樹脂組成物の特性について述べる。 Hereinafter, the characteristics of the epoxy resin composition of the present invention will be described.
　本発明のエポキシ樹脂組成物は、常温（２５℃）での粘度が６０００ｍＰａ・ｓ以下と低く、半導体封止材等の用途で使用する際に作業性が良好である。
　本発明のエポキシ樹脂組成物は、常温（２５℃）での粘度が５５００ｍＰａ・ｓ以下であることが好ましく、４０００ｍＰａ・ｓ以下であることがより好ましく、３０００ｍＰａ・ｓ以下であることがさらに好ましい。 The epoxy resin composition of the present invention has a low viscosity at room temperature (25 ° C.) of 6000 mPa · s or less, and has good workability when used in applications such as a semiconductor sealing material.
The epoxy resin composition of the present invention has a viscosity at normal temperature (25 ° C.) of preferably 5500 mPa · s or less, more preferably 4000 mPa · s or less, and still more preferably 3000 mPa · s or less.
　本発明のエポキシ樹脂組成物は、低温短時間硬化性に優れており、１５０℃以下の温度で数分間の加熱（例えば、１２０℃で３分間の加熱）で硬化することができる。
　本発明のエポキシ樹脂組成物は、後述する実施例に記載の手順で測定されるゲルタイムが１８０秒以下であることが好ましく、９０秒以下であることがより好ましく、６０秒以下であることがさらに好ましい。 The epoxy resin composition of the present invention has excellent low-temperature and short-time curability, and can be cured by heating at a temperature of 150 ° C. or lower for several minutes (for example, heating at 120 ° C. for 3 minutes).
The epoxy resin composition of the present invention preferably has a gel time of 180 seconds or less, more preferably 90 seconds or less, and more preferably 60 seconds or less, as measured by the procedure described in the examples described later. preferable.
　また、本発明のエポキシ樹脂組成物は、常温（２５℃）での貯蔵安定性が良好であり、ポットライフが長い。具体的には、２５℃、湿度５０％の環境にて４８時間保存後の粘度が保存前の粘度の１．２倍未満であり、好ましくは、１６８時間保存後の粘度が保存前の粘度の１．２倍未満である。 Moreover, the epoxy resin composition of the present invention has good storage stability at normal temperature (25 ° C.) and a long pot life. Specifically, the viscosity after storage for 48 hours in an environment of 25 ° C. and 50% humidity is less than 1.2 times the viscosity before storage, and preferably the viscosity after storage for 168 hours is the viscosity before storage. It is less than 1.2 times.
　また、本発明のエポキシ樹脂組成物は、密着性に優れており、後述する実施例に記載の手順で測定した剥離強度が、１０ｋｇ以上であり、好ましくは１５ｋｇ以上であり、より好ましくは１７ｋｇ以上である。 Further, the epoxy resin composition of the present invention is excellent in adhesion, and the peel strength measured by the procedure described in the examples described later is 10 kg or more, preferably 15 kg or more, more preferably 17 kg or more. It is.
　また、本発明のエポキシ樹脂組成物は、ガラス転移温度（Ｔｇ）が、１２０℃以上であることから、封止時のはんだボール補強性に優れ、サーマルサイクル試験（例えば、－４０℃から１２５℃までのサーマルサイクルを繰り返す耐久性試験）においてクラック発生が抑制される。本発明のエポキシ樹脂組成物は、ガラス転移温度（Ｔｇ）が１２５℃以上であることが好ましく、より好ましくは１３０℃以上である。 In addition, since the epoxy resin composition of the present invention has a glass transition temperature (Tg) of 120 ° C. or higher, it has excellent solder ball reinforcement at the time of sealing, and a thermal cycle test (eg, −40 ° C. to 125 ° C. In the durability test of repeating the thermal cycle up to, the occurrence of cracks is suppressed. The epoxy resin composition of the present invention preferably has a glass transition temperature (Tg) of 125 ° C. or higher, more preferably 130 ° C. or higher.
　これらの特性により、本発明のエポキシ樹脂組成物は、一次実装用あるいは二次実装用の半導体封止材として好適である。
　本発明のエポキシ樹脂組成物は、接着剤やダイボンディング剤にも好適である。 Due to these characteristics, the epoxy resin composition of the present invention is suitable as a semiconductor sealing material for primary mounting or secondary mounting.
The epoxy resin composition of the present invention is also suitable for adhesives and die bonding agents.
　以下、実施例により、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
（実施例１～１４、比較例１～４）
　下記表に示す配合割合となるように、ロールミルを用いて原料を混練して実施例１～１４、比較例１～４のエポキシ樹脂組成物を調製した。なお、表中の各組成に関する数値は質量部を表している。
　なお、表中の記号は、それぞれ以下を表わす。
エポキシ樹脂：ビスフェノールＡ型エポキシ樹脂、製品名ＥＸＡ８５０ＣＲＰ、ＤＩＣ株式会社製）
ＤＭＥ：１，４－シクロヘキサンジメタノールジグリシジルエーテル、製品名ＺＸ１６５８ＧＳ、新日鐵化学株式会社製
潜在性硬化剤（イミダゾール系潜在性硬化剤）：マイクロカプセル型イミダゾール（イミダゾール成分とビスフェノールＡ型エポキシ樹脂とを含有）、製品名ＨＸ３７４２、旭化成イーマテリアルズ株式会社製
フェノール樹脂：アリルアクリルフェノール樹脂、製品名ＭＥＨ８００５、明和化成株式会社製
酸無水物系硬化剤：（製品名：ＨＮ－５５００、日立化成工業株式会社製） (Examples 1 to 14, Comparative Examples 1 to 4)
Epoxy resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were prepared by kneading the raw materials using a roll mill so that the blending ratios shown in the following table were obtained. In addition, the numerical value regarding each composition in a table | surface represents the mass part.
In addition, the symbol in a table | surface represents the following, respectively.
Epoxy resin: bisphenol A type epoxy resin, product name EXA850CRP, manufactured by DIC Corporation)
DME: 1,4-cyclohexanedimethanol diglycidyl ether, product name ZX1658GS, latent curing agent (imidazole-based latent curing agent) manufactured by Nippon Steel Chemical Co., Ltd .: microcapsule type imidazole (imidazole component and bisphenol A type epoxy resin) ), Product name HX3742, phenol resin manufactured by Asahi Kasei E-materials Co., Ltd .: allyl acrylic phenol resin, product name MEH8005, acid anhydride curing agent manufactured by Meiwa Kasei Co., Ltd .: (product name: HN-5500, Hitachi Chemical) Manufactured by Kogyo Corporation)
　調製したエポキシ樹脂組成物について、以下の評価を実施した。
（硬化物外観）
　評価用試料を、ポリイミドフィルムの上に接着したシリコンチップ（２×２０×０．７５ｍｍ）の長辺側面に接するように１０ｍｇ塗布した試験片をオーブンへ入れ、１２０℃で３ｍｉｎ加熱し、エポキシ樹脂組成物を硬化させた。加熱後の硬化物外観を目視観察した。硬化物にしわ・柚子肌等の外観不良や色むらが認められなかった場合を○とし、硬化物にしわ・柚子肌等の外観不良や色むらが認められた場合を×とした。
（粘度、ポットライフ）
　ＥＭＤ型粘度計（トキメック社製、機器名：ＴＶ－２２を用いて、液温２５℃、１ｒｐｍで調製直後の評価用試料の粘度（初期粘度）を測定した。
　その後、評価用試料を密閉容器に入れて２５℃、湿度５０％の環境にて４８時間保管した時点における粘度を測定した。４８時間保管後の粘度が初期粘度の１．２倍未満の場合を○とし、１．２倍以上であった場合を×とした。
　また、評価用試料を密閉容器に入れて２５℃、湿度５０％の環境にて１６８時間保管した時点における粘度を測定した。１６８時間保管後の粘度が初期粘度の１．２倍未満の場合を○とし、１．２倍以上であった場合を×とした。
（ゲルタイム）
　１２０℃の熱板上に、エポキシ樹脂組成物を５ｍｇ±１ｍｇを供給し、攪拌棒によって円を描くようにして攪拌し、供給時から、攪拌しながら攪拌棒を持ち上げて引き離した場合に糸引きが５ｍｍ以下となるまでの時間を測定した。
（密着性）
　ガラエポ基板に評価用試料を印刷し、該試料上に２ｍｍ×２ｍｍのシリコンチップを載置する。これを１５０±２℃の熱風乾燥機で５ｍｉｎ加熱硬化させる。これを試験片とし、ｄａｇｅ社製万能型ボンドテスター「ＤＡＧＥ４０００」を用いてシリコンチップに荷重をかけ、チップが剥離した時の強度（剥離強度）を測定する。ｎ＝１０とし、その平均値を検査値とする。 The following evaluation was implemented about the prepared epoxy resin composition.
(Appearance of cured product)
A test piece in which 10 mg of the sample for evaluation was applied so as to be in contact with the long side surface of the silicon chip (2 × 20 × 0.75 mm) adhered on the polyimide film was put in an oven, heated at 120 ° C. for 3 minutes, and epoxy resin The composition was cured. The appearance of the cured product after heating was visually observed. The case where the cured product had no appearance defects or color irregularities such as wrinkles or cocoon skin was marked with ◯, and the case where the cured product had appearance defects or color irregularities such as wrinkles was marked with x.
(Viscosity, pot life)
Using an EMD viscometer (manufactured by Tokimec Co., Ltd., device name: TV-22), the viscosity (initial viscosity) of an evaluation sample immediately after preparation was measured at a liquid temperature of 25 ° C. and 1 rpm.
Thereafter, the viscosity at the time when the sample for evaluation was put in a sealed container and stored for 48 hours in an environment of 25 ° C. and 50% humidity was measured. The case where the viscosity after storage for 48 hours was less than 1.2 times the initial viscosity was marked with ◯, and the case where it was 1.2 times or more was marked with x.
Moreover, the viscosity at the time of putting the sample for evaluation in an airtight container and storing it in an environment of 25 ° C. and a humidity of 50% for 168 hours was measured. The case where the viscosity after storage for 168 hours was less than 1.2 times the initial viscosity was rated as ◯, and the case where it was 1.2 times or more was rated as x.
(Geltime)
When 5 mg ± 1 mg of the epoxy resin composition is supplied on a hot plate at 120 ° C., stir in a circle with a stirring bar, and when the stirring bar is lifted and pulled away while being stirred, the thread is pulled Was measured until the time became 5 mm or less.
(Adhesion)
An evaluation sample is printed on a glass epoxy substrate, and a 2 mm × 2 mm silicon chip is placed on the sample. This is heat-cured for 5 minutes with a hot air dryer at 150 ± 2 ° C. Using this as a test piece, a load is applied to the silicon chip using a universal bond tester “DAGE 4000” manufactured by dage, and the strength (peel strength) when the chip peels is measured. n = 10, and the average value is used as the inspection value.
　ガラス転移温度（Ｔｇ）：１２０℃で３ｍｉｎ加熱硬化させた硬化物について、真空理工社製、ＴＭ３０００を用いて、ＴＭＡ法によりガラス転移温度を測定した。 Glass transition temperature (Tg): The glass transition temperature of the cured product that was heat-cured at 120 ° C. for 3 minutes was measured by the TMA method using TM3000 manufactured by Vacuum Riko Co., Ltd.
Figure JPOXMLDOC01-appb-T000001
 実施例１
（Ｂ）成分　３１．１質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　５．６質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例２
（Ｂ）成分　３１．２質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１１．２質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例３
（Ｂ）成分　３１．２質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５．０質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例４
（Ｂ）成分　３１．３質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１８．８質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例５
（Ｂ）成分　３１．２質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　２４．３質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例６
（Ｂ）成分　３１．２質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　１．０質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例７
（Ｂ）成分　３１．２質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　３．１質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
Figure JPOXMLDOC01-appb-T000001
 Example 1
(B) component 31.1 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 5.6 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 2
(B) component 31.2 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
Component (C) (imidazole component) 11.2% by mass
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 3
(B) component 31.2 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15.0 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 4
(B) component 31.3 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 18.8 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 5
(B) component 31.2 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 24.3 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 6
(B) component 31.2 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) Component 1.0 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 7
(B) component 31.2 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 3.1 mass%
(Based on the total mass of all components of the epoxy resin composition)
Figure JPOXMLDOC01-appb-T000002
 実施例８
（Ｂ）成分　３１．２質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　９．４質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例９
（Ｂ）成分　３１．１質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　１４．７質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例１０
（Ｂ）成分　３１．０質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　２０．１質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例１１
（Ｂ）成分　５．０質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例１２
（Ｂ）成分　１０．０質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例１３
（Ｂ）成分　５０．０質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
実施例１４
（Ｂ）成分　６２．５質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
Figure JPOXMLDOC01-appb-T000002
 Example 8
(B) component 31.2 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 9.4 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 9
(B) component 31.1 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) Component 14.7 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 10
(B) component 31.0 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 20.1 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 11
(B) component 5.0 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 12
(B) component 10.0 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 13
(B) component 50.0 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Example 14
(B) component 62.5 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Figure JPOXMLDOC01-appb-T000003
比較例１
（Ｂ）成分　３１．１質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　３．０質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
比較例２
（Ｂ）成分　３１．２質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　０質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
比較例３
（Ｂ）成分　０質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　１５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
（Ｄ）成分　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
比較例４
（Ｂ）成分　２９．１質量％
（（Ａ）（（Ｃ）のエポキシ樹脂成分を含む），（Ｂ）成分の合計質量に対して）
（Ｃ）成分（イミダゾール成分）　５質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
　比較例４は、マイクロカプセル型イミダゾールを硬化促進剤として使用する場合の通常量含有させたものであり、硬化剤としては酸無水物系硬化剤を組成物中のエポキシ樹脂成分に対する当量比で０．６当量含有する。
（Ｄ）成分　０質量％
（エポキシ樹脂組成物の全成分の合計質量に対して）
Figure JPOXMLDOC01-appb-T000003
Comparative Example 1
(B) component 31.1 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 3.0 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Comparative Example 2
(B) component 31.2 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 0 mass%
(Based on the total mass of all components of the epoxy resin composition)
Comparative Example 3
(B) component 0 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 15 mass%
(Based on the total mass of all components of the epoxy resin composition)
(D) component 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
Comparative Example 4
(B) component 29.1 mass%
((A) (including the epoxy resin component of (C)), (B) with respect to the total mass of the component)
(C) component (imidazole component) 5 mass%
(Based on the total mass of all components of the epoxy resin composition)
In Comparative Example 4, a microcapsule type imidazole is used in a usual amount when used as a curing accelerator, and an acid anhydride curing agent is used as a curing agent in an equivalent ratio of 0 to an epoxy resin component in the composition. .6 equivalents.
(D) component 0 mass%
(Based on the total mass of all components of the epoxy resin composition)
　実施例１～１４のエポキシ樹脂組成物は、硬化物外観が良好であり、均一な硬化が行われたことが確認された。また、２５℃における粘度が６０００ｍＰａ・ｓ以下であった。また、ゲルタイムが１２０ｓ以下であり、低温短時間硬化性に優れることが確認された。また、密着性が良好であり、ガラス転移温度（Ｔｇ）も１２０℃以上であった。また、４８時間保管後のポットライフも良好であった。
（Ｃ）成分の含有量が５．６～２４．３質量％、（Ｄ）成分の含有量が１～２０．１質量％の実施例１～４、６～９、１１～１４は１６８時間保管後のポットライフも良好であった。
　一方、（Ｃ）成分の含有量が５質量％未満の比較例１のエポキシ樹脂組成物は、ゲルタイム評価で１８０ｓ経過後でも硬化せず、低温短時間硬化性に劣ることが確認された。このため、硬化物外観と密着性の評価は実施しなかった。（Ｄ）成分を含まない比較例２は硬化物外観が劣っており、均一な硬化を行うことができなかったことが確認された。このため、密着性の評価とガラス転移温度の測定は実施しなかった。（Ｂ）成分を含まない比較例３は２０℃における粘度が６０００ｍＰａ・ｓ超と高かった。（Ｄ）成分を含まず、酸無水物系硬化剤を使用し、マイクロカプセル型イミダゾールを硬化促進剤として使用する場合の通常量含有させた比較例４は、ゲルタイム評価で１８０ｓ経過後でも硬化せず、低温短時間硬化性に劣ることが確認された。この理由としては、酸無水物系硬化剤の存在によって、イミダゾールによる硬化作用が遅延されたことによるものと考える。なお、低温短時間硬化性に劣ることが確認されたため、密着性評価は実際しなかった。また、４８時間保管後のポットライフが劣っていた。このため、１６８時間保管後のポットライフの評価は実施しなかった。 It was confirmed that the epoxy resin compositions of Examples 1 to 14 had a good cured product appearance and were uniformly cured. Moreover, the viscosity in 25 degreeC was 6000 mPa * s or less. Moreover, it was confirmed that the gel time is 120 s or less and the low-temperature short-time curability is excellent. Moreover, adhesiveness was favorable and the glass transition temperature (Tg) was 120 degreeC or more. The pot life after storage for 48 hours was also good.
In Examples 1-4, 6-9, and 11-14 in which the content of the component (C) is 5.6 to 24.3 mass% and the content of the component (D) is 1 to 20.1 mass% is 168 hours The pot life after storage was also good.
On the other hand, it was confirmed that the epoxy resin composition of Comparative Example 1 having a content of the component (C) of less than 5% by mass did not cure even after 180 s in gel time evaluation and was inferior in low-temperature short-time curability. For this reason, evaluation of hardened | cured material external appearance and adhesiveness was not implemented. (D) The comparative example 2 which does not contain a component was inferior in hardened | cured material external appearance, and it was confirmed that uniform hardening was not able to be performed. For this reason, the evaluation of adhesion and the measurement of the glass transition temperature were not carried out. In Comparative Example 3 containing no component (B), the viscosity at 20 ° C. was as high as over 6000 mPa · s. In Comparative Example 4, which does not contain the component (D), uses an acid anhydride curing agent, and contains a normal amount of microcapsule type imidazole as a curing accelerator, it is cured even after 180 s in gel time evaluation. Thus, it was confirmed that the low temperature short time curability was inferior. The reason for this is considered to be that the curing action by imidazole was delayed by the presence of the acid anhydride curing agent. In addition, since it was confirmed that it was inferior to low temperature short time curability, adhesive evaluation was not actually carried out. Moreover, the pot life after 48 hours storage was inferior. For this reason, pot life evaluation after storage for 168 hours was not performed.

Claims (6)

  1. 　（Ａ）エポキシ樹脂、（Ｂ）１，４－シクロヘキサンジメタノールジグリシジルエーテル、（Ｃ）イミダゾール系潜在性硬化剤、および、（Ｄ）フェノール樹脂よりなり、
    　前記（Ａ）エポキシ樹脂および前記（Ｂ）１，４－シクロヘキサンジメタノールジグリシジルエーテルの合計質量に対する前記（Ｂ）１，４－シクロヘキサンジメタノールジグリシジルエーテルの含有量が０．５～８０質量％であり、エポキシ樹脂組成物の全成分の合計質量に対する前記（Ｃ）イミダゾール系潜在性硬化剤の含有量が５～２５質量％であり、エポキシ樹脂組成物の全成分の全成分の合計質量に対する前記（Ｄ）フェノール樹脂の含有量が０．５～２５質量％であることを特徴とするエポキシ樹脂組成物。     (A) epoxy resin, (B) 1,4-cyclohexanedimethanol diglycidyl ether, (C) imidazole-based latent curing agent, and (D) phenol resin,
    The content of the (B) 1,4-cyclohexanedimethanol diglycidyl ether is 0.5 to 80% by mass with respect to the total mass of the (A) epoxy resin and the (B) 1,4-cyclohexanedimethanol diglycidyl ether. The content of the (C) imidazole-based latent curing agent with respect to the total mass of all components of the epoxy resin composition is 5 to 25% by mass, and is based on the total mass of all components of the epoxy resin composition An epoxy resin composition, wherein the content of the (D) phenol resin is 0.5 to 25% by mass.
  2. 　前記（Ａ）エポキシ樹脂として、液状エポキシ樹脂を含有する、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, comprising a liquid epoxy resin as the (A) epoxy resin.
  3. 　さらに（Ｅ）ホウ酸エステル化合物を含有する請求項１または２に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1 or 2, further comprising (E) a borate compound.
  4. 　さらに、（Ｆ）シリカフィラーを含有する請求項１～３のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 3, further comprising (F) a silica filler.
  5. 　さらに、（Ｇ）シランカップリング剤を含有する請求項１～４のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 4, further comprising (G) a silane coupling agent.
  6. 　請求項１～５のいずれかに記載のエポキシ樹脂組成物を用いた半導体封止材。 A semiconductor sealing material using the epoxy resin composition according to any one of claims 1 to 5.
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