Classifications

• • 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Epoxy Resins (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
• Power Engineering (AREA)
• General Physics & Mathematics (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Computer Hardware Design (AREA)
• Engineering & Computer Science (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Physics & Mathematics (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=46602309

Family Applications (1)

Country Status (6)

Cited By (4)

Families Citing this family (12)

Citations (5)

Family Cites Families (4)

• 2011
  • 2011-02-03 JP JP2011021363A patent/JP4965715B1/ja active Active
  • 2011-08-02 MY MYPI2013002887A patent/MY161359A/en unknown
  • 2011-08-02 CN CN201180065777.0A patent/CN103328530B/zh active Active
  • 2011-08-02 WO PCT/JP2011/067640 patent/WO2012105072A1/ja active Application Filing
  • 2011-08-02 KR KR1020137019593A patent/KR101819264B1/ko active IP Right Grant
  • 2011-08-05 TW TW100127977A patent/TWI547520B/zh active

Patent Citations (5)

Also Published As

Similar Documents

Legal Events