Classifications

• • 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
  • C08L63/04—Epoxynovolacs
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
  • C08K7/18—Solid spheres inorganic
• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08G59/68—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 catalysts used
  • C08G59/688—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 catalysts used containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
• • 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
  • H01L23/295—Organic, e.g. plastic containing a filler
• • 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
  • H01L23/296—Organo-silicon compounds
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/006—Additives being defined by their surface area
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2003/1034—Materials or components characterised by specific properties
  • C09K2003/1078—Fire-resistant, heat-resistant materials
• • 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 molding material for sealing and an electronic component device including an element sealed with the molding material.
• soldering temperature soldering temperature
• silane coupling agents have been examined by focusing on improvement in adhesiveness with an insert such as an element lead frame.
• an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent for example, see Japanese Patent Application Laid-Open (JP-A) No. H11-147939
• a sulfur atom-containing silane coupling agent for further adhesiveness improvement for example, see JP-A No. 2000-103940.
• the present invention has been accomplished under the circumstance in view. It is an object of the present invention to provide an epoxy resin molding material for sealing excellent in reflow resistance and moldability without reducing flame retardancy and an electronic component device including an element sealed with the material.
• the present invention relates to an epoxy resin molding material for sealing including both a specific amino group-containing silane compound and a specific epoxy group-containing silane compound, and an electronic component device including an element sealed with the epoxy resin molding material for sealing. More specifically, the present invention is as follows:
• the present invention relates to (1) an epoxy resin molding material for sealing including (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, (E1) an arylamino group-containing alkoxysilane compound, and (E2) an epoxy group-containing alkoxysilane compound.
• the present invention relates to (2) the epoxy resin molding material for sealing according to the (1), in which (E1) the arylamino group-containing alkoxysilane compound is a compound represented by the following general formula (I).
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent; p represents an integer from 1 to 3; and q represents 2 or 3.
• the present invention relates to (3) the epoxy resin molding material for sealing according to the (1) or the (2), in which (E2) the epoxy group-containing alkoxysilane compound is at least one compounds represented by the following general formulas (II) or (III).
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent; p represents an integer from 1 to 3; and q represents 2 or 3; and
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent; p represents an integer from 1 to 3; and q represents 2 or 3.
• the present invention relates to (4) the epoxy resin molding material for sealing according to any one of the (1) to the (3), in which a total amount of (E1) the arylamino group-containing alkoxysilane compound in the epoxy resin molding material for sealing is from 10% by mass to 80% by mass with respect to a total amount of (E1) the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxy silane compound in the epoxy resin molding material for sealing.
• the present invention relates to (5) the epoxy resin molding material for sealing according to any one of the (1) to the (4), in which (E1) the total amount of the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxy silane compound in the epoxy resin molding material for sealing is from 2% by mass to 15% by mass with respect to a total amount of (A) the epoxy resin in the epoxy resin molding material for sealing.
• the present invention relates to (6) an electronic component device including an element sealed with the epoxy resin molding material for sealing according to any one of the (1) to the (5).
• the present invention can provide an epoxy resin molding material for sealing having excellent reflow resistance and moldability without reducing flame retardancy, and an electronic component device including an element sealed with the material. Therefore, the present invention has great industrial value.
• a numerical range represented by “to” indicates a range including numerical values before and after “to” as the minimum value and the maximum value, respectively.
• the amount of the each ingredient in the composition means a total amount of the plural substances present in the composition, unless otherwise specified.
• An epoxy resin molding material for sealing of the present invention includes (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, (E1) an arylamino group-containing alkoxysilane compound, and (E2) an epoxy group-containing alkoxy silane compound, and, as needed, is formed by including other ingredients.
• the material for sealing is excellent in reflow resistance and moldability.
• the epoxy resin molding material for sealing is preferably a solid epoxy resin composition that is a solid at room temperature (25° C.), whereby the material for sealing is excellent in preservation stability.
• the shape of the solid is not particularly limited and the solid can be of any shape, such as powder, granules, or tablets.
• the epoxy resin molding material for sealing of the present invention includes (E1) an arylamino group-containing alkoxysilane compound.
• (E2) an epoxy group-containing alkoxysilane compound reacts with an amino group, it is thus difficult to assume that an epoxy group-containing alkoxysilane compund is used together with an amino group-containing compound.
• (E1) the arylamino group-containing alkoxysilane compound even when mixed with (E2) the epoxy group-containing alkoxysilane compound, the reduction of preservation stability of the mixture is suppressed, thereby suppressing viscosity increase and gelation of the mixture.
• each of (E1) the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxysilane compound exhibits function thereof, obtaining an epoxy resin molding material for sealing excellent in reflow resistance and moldability.
• the structure of (E1) the arylamino group-containing alkoxysilane compound in the present invention is not particularly limited as long as the compound is an alkoxysilane compound having an aryl group adjacent to an amino group.
• Examples of (E1) the arylamino group in the arylamino group-containing alkoxysilane compound include phenylamino groups and naphthylamino groups.
• hydrogen atoms of phenylamino groups and naphthylamino groups each independently may be substituted with a hydrocarbon group having 1 to 9 carbon atoms, an amino group, an aminophenyl group, or an aminonaphtyl group.
• Examples of the hydrocarbon group having 1 to 9 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a vinyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a methylbenzyl group, an ethylbenzyl group and a vinylbenzyl group.
• (E1) the arylamino group-containing alkoxysilane compound in the present invention has a structure represented by the following general formula (I).
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent; p represents an integer from 1 to 3; and q represents 2 or 3.
• Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R 1 and R 2 in the general formula (I) include linear, branched, and cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group and a hexyl group, alkenyl groups such as a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group, and a phenyl group. Hydrogen atoms of these hydrocarbon groups may be substituted.
• the hydrocarbon group may have a substituent.
• substituents in the hydrocarbon groups include a hydroxy group, alkoxy groups having 1 to 6 carbon atoms, and an acetoxy group.
• the hydrocarbon group having 1 to 6 carbon atoms represented by R 1 and R 2 is, from the viewpoint of fluidity and adhesiveness, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and from the viewpoint of easy availability, still more preferably a methyl group.
• p in the general formula (I) represents, from the viewpoint of fluidity and adhesiveness, preferably 2 or 3, and from the viewpoint of easy availability, more preferably 3.
• q in the general formula (I) represents preferably 3, from the viewpoint of preservation stability and easy availability of the silane compound.
• Any one of these (E1) arylamino group-containing alkoxysilane compounds may be used alone or two or more thereof may be used in combination.
• the arylamino group-containing alkoxysilane compound such as ⁇ -aminopropyltriethoxysilane
• fluidity and reflow resistance are deteriorated
• the epoxy group-containing alkoxy silane compound when mixed with (E2) the epoxy group-containing alkoxy silane compound, the preservation stability of the mixture is significantly deteriorated, thereby easily causing viscosity increase and gelation of the mixture.
• the epoxy resin molding material for sealing of (E2) the present invention includes an epoxy group-containing alkoxy silane compound.
• the structure of the epoxy group-containing alkoxy silane compound is not particularly limited as long as the compound is an alkoxysilane silane compound having an epoxy group.
• the epoxy group-containing alkoxy silane compound used in the present invention is preferably at least one compounds represented by the following general formulas (II) or (III):
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent; p represents an integer from 1 to 3; and q represents 2 or 3.
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may have a substituent; p represents an integer from 1 to 3; and q represents 2 or 3.
• Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R 1 and R 2 in the general formulas (II) and (III) include linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group and a hexyl group, alkenyl groups such as a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group, and a phenyl group.
• linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group and
• the hydrocarbon group may have a substituent.
• substituents in the hydrocarbon group include a hydroxy group, alkoxy groups having 1 to 6 carbon atoms and an acetoxy group.
• the hydrocarbon group having 1 to 6 carbon atoms represented by R 1 and R 2 is, particularly from the viewpoint of fluidity and adhesiveness, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and from the viewpoint of easy availability, still more preferably a methyl group.
• p in the general formulas (II) and (III) represents, from the viewpoint of fluidity and adhesiveness, preferably 2 or 3, and from the viewpoint of easy availability, represents more preferably 3.
• q in the general formula (II) represents, from the viewpoint of preservation stability and easy availability of the silane compound, preferably 3.
• q in the general formula (III) represents, from the viewpoint of preservation stability and easy availability of the silane compound, preferably 2.
• Examples of such (E2) an epoxy group-containing alkoxysilane compound available as a commercialized product include Z-6040 (3-glycidoxypropyl trimethoxysilane), Z-6041 (3-glycidoxypropyl triethoxysilane), Z-6042 (3-glycidoxypropylmethyl diethoxysilane), Z-6043 (2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane), and Z-6044 (3-glycidoxypropylmethyl dimethoxysilane) manufactured by Toray DowCorning Co., Ltd.
• any one of these (E2) epoxy group-containing alkoxysilane compounds may be used alone or two or more thereof may be used in combination.
• two or more (E2) epoxy group-containing alkoxysilane compounds only the compound represented by the general formula (II) may be used, only the compound represented by the general formula (III) may be used, or the compound represented by the general formula (II) and the compound represented by the general formula (III) may be used in combination.
• E1 content percentage when a total amount of (E1) the arylamino group-containing alkoxysilane compound in the epoxy resin molding material for sealing with respect to a total amount of (E1) the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxysilane compound in the epoxy resin molding material for sealing is regarded as “E1 content percentage”, the E1 content percentage is not particularly limited as long as the advantageous effects of the present invention are not impaired.
• the E1 content percentage is preferably from 5% by mass to 90% by mass, and from the viewpoint of reduction of elastic modulus and improvement in reflow resistance, more preferably from 10% by mass to 80% by mass, and still more preferably from 20% by mass to 60% by mass.
• the E1+E2 content percentage is not particularly limited as long as the advantageous effects of the present invention are not impaired.
• the E1+E2 content percentage is preferably from 1% by mass to 20% by mass, and from the viewpoint of reflow resistance, more preferably from 2% by mass to 15% by mass, and still more preferably from 4% by mass to 12% by mass.
• the arylamino group-containing alkoxysilane compound to be used is a silane compound of the general formula (I) in which R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, p represents 2 or 3, and q represents 3;
• the epoxy group-containing alkoxysilane compound to be used is at least one of a silane compound of the general formula (II) in which R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms, p represents 2 or 3, and q represents 3, or a silane compound of the general formula (III) in which R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, p represents 2 or 3, and q represents 2;
• the E1 content percentage is from 10% by mass to 80% by mass; and the E1+E2 content percentage is from 2% by mass to 15% by mass.
• the arylamino group-containing alkoxysilane compound to be used is a silane compound of the general formula (I) in which R 1 and R 2 each independently represent a methyl group or an ethyl group, p represents 2 or 3, and q represents 3;
• the epoxy group-containing alkoxysilane compound to be used is at least one of a silane compound of the general formula (II) in which R 1 and R 2 each independently represent a methyl group or an ethyl group, p represents 2 or 3, and q represents 3, or a silane compound of the general formula (III) in which R 1 and R 2 each independently represent a methyl group or an ethyl group, p represents 2 or 3, and q represents 2;
• the E1 content percentage is from 20% by mass to 60% by mass; and the E1+E2 content percentage is from 4% by mass to 12% by mass.
• a method for adding (E1) the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxysilane compound is not particularly limited.
• each of the compounds may be added alone, or (E1) the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxysilane compound may be mixed together in advance and then added.
• the order of addition of the compounds is not particularly limited.
• the epoxy resin used in the present invention is not particularly limited as long as the resin is commonly used in epoxy resin molding materials for sealing. Among them, preferred are epoxy resins including two or more epoxy groups in one molecule thereof.
• epoxy resins include novolac epoxy resins including phenol novolac epoxy resins, ortho-cresol novolac epoxy resins, and epoxy resins having a triphenylmethane structure, which are prepared by epoxidizing novolac resins obtained by condensation or co-condensation of at least one selected from a group consisting of phenols such as a phenol, a cresol, a xylenol, a resorcin, a catechol, a bisphenol A and a bisphenol F, and naphthols such as an ⁇ -naphthol, a ⁇ -naphthol and a dihydroxynaphthalene with an aldehyde group-containing compound such as a formaldehyde, an acetaldehyde
• the epoxy resin preferably includes a biphenyl epoxy resin that is a diglycidyl ether of an alkyl-substituted, aromatic ring-substituted, or unsubstituted biphenol.
• the epoxy resin preferably includes a novolac epoxy resin, and from the viewpoint of low hygroscopicity, preferably includes a dicyclopentadiene epoxy resin.
• the epoxy resin preferably includes a naphthalene epoxy resin, and from the viewpoint of achieving both fluidity and flame retardancy, preferably includes a bisphenol F epoxy resin that is a diglycidyl ether of an alkyl-substituted, aromatic-ring substituted, or unsubstituted bisphenol F.
• the epoxy resin preferably includes a thiodiphenol epoxy resin that is a diglycidyl ether of an alkyl-substituted, aromatic ring-substituted, or unsubstituted thiodiphenol.
• the epoxy resin preferably includes an epoxide of a phenol aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted, or unsubstituted phenol and dimethoxyparaxylene or bis(methoxymethyl)biphenyl.
• the epoxy resin preferably includes an epoxide of a naphthol aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted, or unsubstituted naphthol and dimethoxyparaxylene.
• Examples of the biphenyl epoxy resin include an epoxy resin represented by the following general formula (IV).
• R 1 to R 8 each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; and n represents an integer from 0 to 3.
• R 1 to R 8 in the general formula (IV) include a hydrogen atom; alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a tert-butyl group; alkenyl groups having 1 to 10 carbon atoms such as a vinyl group, an allyl group, and a butenyl group; and alkoxy groups having 1 to 10 carbon atoms such as a methoxy group and an ethoxy groups.
• a hydrogen atom or a methyl group are preferable.
• the biphenyl epoxy resin represented by the general formula (IV) is obtained by reacting a biphenyl compound with epichlorohydrin in a known method.
• Examples of such an epoxy resin include an epoxy resin including, as a main ingredient,
• Examples of commecially available products of such an epoxy resin include YX-4000 and YL-6121H: trade names, manufactued by Mitsubishi Chemical Co., Ltd.
• the content percentage of the biphenyl epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in an amount of an entire epoxy resin in order to allow the epoxy resin to exhibit performance thereof.
• Examples of the thiodiphenol epoxy resin include an epoxy resin represented by the following general formula (V).
• R 1 to R 8 each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; and n represents an integer from 0 to 3.
• R 1 to R 8 in the general formula (V) include a hydrogen atom; alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a tert-butyl group; alkenyl groups having 1 to 10 carbon atoms such as a vinyl group, an allyl group, and a butenyl group; and alkoxy groups having 1 to 10 carbon atoms such as a methoxy group and an ethoxy groups.
• a hydrogen atom, a methyl group or a tert-butyl group are preferable.
• the thiodiphenol epoxy resin represented by the general formula (V) is obtained by reacting a thiodiphenol compound with epichlorohydrin in a known method.
• an epoxy resin include an epoxy resin including, as a main ingredient, a diglycidyl ether of 4,4′-dihydroxydiphenylsulfide, an epoxy resin including, as a main ingredient, a diglycidyl ether of 2,2′,5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfide, and an epoxy resin including, as a main ingredient, a diglycidyl ether of
• the content percentage of the thiodiphenol epoxy resin is 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxy resin to exhibit performance thereof.
• Examples of the bisphenol F epoxy resin include an epoxy resin represented by the following general formula (VI).
• R 1 to R 8 each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; and n represents an integer from 0 to 3.
• R 1 to R 8 in the general formula (VI) include a hydrogen atom; alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a tert-butyl group; alkenyl groups having 1 to 10 carbon atoms such as a vinyl group, an allyl group and a butenyl group; and alkoxy groups having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group.
• a hydrogen atom or a methyl group are preferable.
• the bisphenol F epoxy resin represented by the general formula (VI) is obtained by reacting a bisphenol F compound with epichlorohydrin in a known method.
• an epoxy resin include an epoxy resin including, as a main ingredient, a diglycidyl ether of 4,4′-methylene bis(2,6-dimethylphenol), an epoxy resin including, as a main ingredient, a diglycidyl ether of 4,4′-methylene bis(2,3,6-trimethylphenol), and an epoxy resin including, as a main ingredient, a diglycidyl ether of 4,4′-methylenebisphenol.
• an epoxy resin including the diglycidyl ether of 4,4′-methylene bis(2,6-dimethylphenol) as a main ingredient are examples of a commecially available product of such an epoxy resin.
• a commecially available product of such an epoxy resin include YSLV-80XY: trade name, manufactured by Nippon Steel Chemical Co., Ltd.
• the content percentage of the bisphenol F epoxy resin is 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxy resin to exhibit performance thereof.
• novolac epoxy resin examples include an epoxy resin represented by the following general formula (VII).
• Rs each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; and n represents an integer from 0 to 10.
• Rs in the general formula (VII) represent a hydrogen atom; alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and an isobutyl group; and alkoxy groups having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and more preferably a hydrogen atom or a methyl group.
• n represents an integer from 0 to 3.
• the novolac epoxy resin represented by the general formula (VII) is easily obtained by reacting a novolac phenol resin with epichlorohydrin.
• novolac epoxy resins represented by the general formula (VII) preferred is an ortho-cresol novolac epoxy resin.
• Examples of a commercially available product of such an epoxy resin include ESCN-190: trade name, manufactured by Sumitomo Chemical Co., Ltd.
• the content percentage of the novolac epoxy resin is preferably 20% by mass or more and more preferably 30% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxy resin to exhibit performance thereof.
• dicyclopentadiene epoxy resin examples include an epoxy resin represented by the following general formula (VIII).
• R 1 s each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms
• R 2 s each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms
• n represents an integer from 0 to 10
• m represents an integer from 0 to 6.
• R 1 in the general formula (VIII) examples include a hydrogen atom; and hydrocarbon groups having 1 to 10 carbon atoms, which include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a tert-butyl group, and alkenyl groups such as a vinyl group, an allyl group and a butenyl group. Particularly preferred are alkyl groups such as a methyl group and an ethyl group or a hydrogen atom, and more prefered are a methyl group or a hydrogen atom.
• R 2 examples include unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, which include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a tert-butyl group, and alkenyl groups such as a vinyl group, an allyl group and a butenyl group. Particularly, preferably, m represents 0.
• the content percentage of the dicyclopentadiene epoxy resin is 20% by mass or more, and more preferably 30% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxy resin to exhibit performance thereof.
• naphthalene epoxy resin examples include an epoxy resin represented by the following general formula (IX).
• R 1 to R 3 each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; p represents 1 or 0; m and n each independently represent an integer from 0 to 11 and are selected so that (m+n) represents an integer from 1 to 11 and (m+p) represents an integer from 1 to 12.
• i represents an integer from 0 to 3
• j represents an integer from 0 to 2
• k represents an integer from 0 to 4, respectively.
• R 1 to R 3 in the general formula (IX) include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a tert-butyl group; alkenyl groups having 1 to 10 carbon atoms such as a vinyl group, an allyl group and a butenyl group; and alkoxy groups having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group. Particularly preferred are a methyl group and also, preferably, at least one of i, j and k represents 0.
• Examples of the naphthalene epoxy resin represented by the general formula (IX) include random copolymers randomly including m pieces of constitutional units and n pieces of constitutional units, alternating copolymers alternately including m pieces of constitutional units and n pieces of constitutional units, copolymers regularly including m pieces of constitutional units and n pieces of constitutional units, and block copolymers including m pieces of constitutional units and n pieces of constitutional units in blocks. Any one of these copolymers may be used alone or two or more thereof may be used in combination. Examples of a commercially available product of such an epoxy resin include NC-7300: trade name, manufactured by Nippon Kayaku Co. Ltd.
• the content percentage of the naphthalene epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxy resin to exhibit performance thereof.
• Examples of the epoxide of the phenol aralkyl resin include an epoxy resin represented by the following general formula (X) and an epoxy resin represented by the following general formula (XI).
• R 1 to R 8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms; R 9 each independetly represents a monovalent hydrocarbon group having 1 to 12 carbon atoms; i represents an integer from 0 to 3; and n represents an integer from 0 to 10.
• R 1 to R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms; R 5 each independetly represents a monovalent hydrocarbon group having 1 to 12 carbon atoms; i represents an integer from 0 to 3; and n represents an integer from 0 to 10.
• the epoxide of the biphenylene structure-containing phenol aralkyl resin represented by the general formula (X) is obtained by reacting a phenol aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted, or unsubstituted phenol and bis(methoxymethyl)biphenyl with epichlorohydrin in a known method.
• Examples of the monovalent hydrocarbon group represented by R 1 to R 9 in the general formula (X) include chain alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group; cyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group and a cyclohexenyl group; aryl group-substituted alkyl groups substituted by aryl groups such as a benzyl group and a phenetyl group; alkoxy group-substituted alkyl groups such as methoxy
• n 6 or less on average.
• Examples of a commercially available product of such an epoxy resin include NC-3000S: trade name, manufactured by Nippon Kayaku Co., Ltd.
• an epoxy resin of the general formula (X) in which R 1 to R 8 represent a hydrogen atom and i represents 0 is used in combination with an epoxy resin of the general formula (IV) in which R 1 to R 8 represent a hydrogen atom and n represents 0.
• the epoxide of the phenol aralkyl resin represented by the general formula (XI) is obtained by reacting epichlorohydrin with a phenol aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted, or unsubstituted phenol and dimethoxyparaxylene in a known method.
• Examples of the monovalent hydrocarbon group represented by R 1 to R 5 in the general formula (XI) include chain alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group; cyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group and a cyclohexenyl group; aryl group-substituted alkyl groups substituted by aryl groups such as a benzyl group and a phenetyl group; alkoxy group-substituted alkyl groups such as meth
• R′ to R 4 represent a hydrogen atom, and preferably, i represents 0.
• n represents 6 or less on average. Examples of a commercially available product of such an epoxy resin include NC-2000L: trade name, manufactured by Nippon Kayaku Co., Ltd.
• the content percentage of the epoxide thereof is preferably 20% by mass or more, and more preferably 30% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxide to exhibit performance thereof.
• Examples of the epoxide of the naphthol aralkyl resin include an epoxy resin represented by the following general formula (XII).
• Rs each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms; i represents an integer from 0 to 3; X represents a divalent organic group including an aromatic ring; and n represents an integer from 0 to 10.
• Examples of X include arylene groups such as a phenylene group, a biphenylene group and a naphthylene group; alkyl group-substituted arylene groups such as a tolylene group; alkoxy group-substituted arylene groups; aralkyl group-substituted arylene groups; divalent organic groups derived from aralkyl groups such as a benzyl group and a phenetyl group; and divalent organic groups including an arylene group such as a xylylene group.
• a phenylene group and a biphenylene group are preferred.
• the epoxide of the naphthol aralkyl resin represented by the general formula (XII) is obtained by reacting a naphthol aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted, or unsubstituted naphthol and dimethoxyparaxylene or bis(methoxymethyl)biphenyl with epichlorohydrin in a known method.
• R in the general formula (XII) examples include chain alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group; cyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group; aryl group-substituted alkyl groups such as a benzyl group and a phenetyl group; alkoxy group-substituted alkyl groups such as methoxy group-substituted alkyl groups, ethoxy group
• n 0 or an integer from 1 to 10, and more preferably, represents 6 or less on average.
• epoxide of the naphthol aralkyl resin represented by the general formula (XII) include an epoxide of a naphthol aralkyl resin represented by the following general formula (XIII) and an epoxide of a naphthol aralkyl resin represented by the following general formula (XIV).
• Examples of a commercially available product of the epoxy resin represented by the general formula (XIII) include ESN-375: trade name, manufactured by Nippon Steel Chemical Co., Ltd., and examples of a commercially available product of the epoxy resin represented by the general formula (XIV) include ESN-175: trade name, manufactured by Nippon Steel Chemical Co., Ltd.
• n represents an integer from 0 to 10.
• n represents an integer from 0 to 10.
• the epoxy resin molding material for sealing includes the epoxide of the naphthol aralkyl resin
• the content percentage of the epoxide of the naphthol aralkyl resin is 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxide to exhibit performance thereof.
• the epoxy resin (A) may also be an epoxy resin represented by the following structural formula (XV).
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms; n represents an integer from 0 to 4; and m represents an integer from 0 to 2.
• Examples of the epoxy resin represented by the general formula (XV) include epoxy resins represented by the following general formulas (XVI) to (XXXIV).
• epoxy resins represented by the general formula (XV) from the viewpoint of flame retardancy and moldability, preferred is the epoxy resin represented by the general formula (XVI).
• examples of such a compound available include YX-8800 (trade name, manufactured by Mitsubishi Chemical Co. Ltd).
• the content percentage of the epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more, in an amount of an entire epoxy resin in order to allow the epoxy resin in order to allow the epoxy resin to exhibit performance thereof from various viewpoints.
• the epoxy resin (A) may also be an epoxy resin represented by the following structural formula (XXXXV).
• R 1 and R 2 each independently represent a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 or 2 carbon atoms; and n represents an integer from 0 to 10.
• R 1 and R 2 in the general formula (XXXXV) include chain alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group; cyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group and a cyclohexenyl group; benzyl group; a phenetyl group; alkoxyl groups such as a methoxy group and an ethoxy group. Among them, preferably, R 1 represents a methyl group and R 2 represents a methoxy group. Examples of
• the content percentage of the epoxy resin represented by the general formula (XXXXV) is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in the amount of the entire epoxy resin in order to allow the epoxy resin to exhibit performance thereof.
• the epoxy equivalent weight of the epoxy resin is not particularly limited. Particularly, from the viewpoint of the balance between the various characteristics such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent weight thereof is preferably from 100 g/eq to 1000 g/eq., and more preferably from 150 g/eq to 500 g/eq.
• the softening point or melting point of the epoxy resin is not particularly limited. Particularly, from the viewpoint of moldability and reflow resistance, the softening point or melting point thereof is preferably from 40° C. to 180° C., and from the viewpoint of handleability during producing the epoxy resin molding material for sealing, more preferably from 50° C. to 130° C.
• the content percentage of the epoxy resin (A) in the epoxy resin molding material for sealing is not particularly limited. From the viewpoint of the balance between the various characteristics such as moldability, reflow resistance, and electrical reliability, the content percentage thereof is preferably from 0.4% by mass to 28% by mass, and more preferably from 1.1% by mass to 26% by mass, in a total mass of the epoxy resin molding material for sealing.
• the epoxy resin molding material for sealing includes at least one curing agent.
• the curing agent is not particularly limited as long as the agent is commonly used in epoxy resin molding materials for sealing.
• the curing agent include a novolac phenol resin obtained by condensation or co-condensation of at least one selected from a group consisting of phenols such as a phenol, a cresol, a xylenol, a resorcin, a catechol, a bisphenol A, a bisphenol F, a phenylphenol, a thiodiphenol and aminophenol, and naphthols such as an ⁇ -naphthol, a ⁇ -naphthol, and a dihydroxynaphthalene with a compound having an aldehyde group such as a formaldehyde, a benzaldehyde or a salicylaldehyde in the presence of an acidic catalyst; a phenol aralkyl resin synthesized
• an aralkyl phenol resin such as a naphthol aralkyl resin; a copolymer phenol aralkyl resin including phenol novolac structures and phenol aralkyl structures repeating randomly, in blocks or alternately; a paraxylylene-modified phenol resin; a metaxylylene-modified phenol resin; a melamine-modified phenol resin; a terpene-modified phenol resin; a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified phenol resin; a cyclopentadiene-modified phenol resin; and a polycyclic aromatic ring-modified phenol resin. Any one of these may be used alone or two or more thereof may be used in combination.
• the curing agent includes at least one of the phenol resins.
• phenol aralkyl resins examples include a resin represented by the following general formula (XXXV).
• Rs each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms; i represents an integer from 0 to 3; X represents a divalent organic group including an aromatic ring; and n represents an integer from 0 to 10.
• substituent in the hydrocarbon group include an aryl group, an alkoxy group, an amino group and a hydroxyl group.
• R in the general formula (XXXV) include chain and branched chain alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group; cyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group and a cyclohexenyl group; aryl group-substituted alkyl groups such as a benzyl group and a phenetyl group; alkoxy group-substituted alkyl groups such as methoxy group-substituted alkyl groups
• X represents a divalent organic group including an aromatic ring.
• arylene groups such as a phenylene group, a biphenylene group and a naphthylene group
• alkyl group-substituted arylene groups such as a tolylene group
• alkoxy group-substituted arylene groups divalent organic groups derived from aralkyl groups such as a benzyl group and a phenetyl group
• divalent organic groups including arylene groups such as aralkyl group-substituted arylene groups and xylylene groups.
• substituted or unsubstituted biphenylene groups such as a phenol aralkyl resin represented by the following general formula (XXXVI).
• substituted or unsubstituted phenylene groups such as a phenol aralkyl resin represented by the following general formula (XXXVII).
• n represents an integer from 0 to 10 and preferably represents 6 or less on average.
• Examples of a commercially available product of the biphenylene structure-containing phenol aralkyl resin represented by the general formula (XXXVI) include MEH-7851: trade name, manufactured by Meiwa Plastic Industries Ltd.
• examples of a commercially available product of the phenol aralkyl resin represented by the general formula (XXXVII) include XLC: trade name, manufactured by Mitsui Chemicals Inc.
• the content percentage of the phenol aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in an amount of an entire curing agent in order to allow the resin to exhibit performance thereof.
• naphthol aralkyl resin examples include a resin represented by the following general formula (XXXVIII).
• Rs each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms; i represents an integer from 0 to 3; X represents a divalent organic group including an aromatic ring; and n represent an integer from 0 to 10.
• substituent in the hydrocarbon group include an aryl group, an alkoxy group, an amino group, and a hydroxyl gorup.
• R in the general formula (XXXVIII) include chain and branched chain alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group; cyclic alkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group and a cyclohexenyl group; aryl group-substituted alkyl groups such as a benzyl group and a phenetyl group; alkoxy group-substituted alkyl groups such as methoxy group-substituted alkyl
• X represents a divalent organic group including an aromatic ring.
• arylene groups such as a phenylene group, a biphenylene group and a naphthylene group
• alkyl group-substituted arylene groups such as a tolylene group
• alkoxy group-substituted arylene groups aralkyl group-substituted arylene groups
• divalent organic groups derived from aralkyl groups such as a benzyl group and a phenetyl group
• divalent organic groups including arylene groups such as a xylylene group such as a xylylene group.
• a naphthol aralkyl resin examples include a naphthol aralkyl resin represented by the following general formula (XXXIX) and a naphthol aralkyl resin represented by the following general formula (XXXX).
• XXXIX a naphthol aralkyl resin represented by the following general formula (XXXI)
• XXXX a naphthol aralkyl resin represented by the following general formula (XXXX).
• n represents an integer from 0 to 10 and more preferably represents 6 or less on average.
• Examples of a commercially available product of the naphthol aralkyl resin represented by the general formula (XXXIX) include SN-475: trade name, manufactured by Nippon Steel Chemical Co., Ltd.
• examples of a commercially available product of the naphthol aralkyl resin represented by the general formula (XXXX) include SN-170: trade name, manufactured by Nippon Steel Chemical Co., Ltd.
• the content percentage of the naphthol aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in the amount of the entire curing agent in order to allow the resin to exhibit performance thereof.
• the phenol aralkyl resin represented by the general formula (XXXV) and the naphthol aralkyl resin represented by the general formula (XXXVIII) are partially or entirely pre-mixed with a polymerizable monomer such as acenaphthylene.
• a polymerizable monomer such as acenaphthylene.
• Acenaphthylene can be obtained by dehydrogenation of acenaphthene, but a commercially available product thereof may be used.
• a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin can be used instead of acenaphthylene.
• Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization.
• a conventionally known catalyst can be used, but only heat can be used without any catalyst.
• polymerization temperature is preferably from 80° C. to 160° C., and more preferably from 90° C. to 150° C.
• the polymer of acenaphthylene obtained or the polymer of acenaphthylene and another aromatic olefin obtained has a softening point of preferably from 60° C. to 150° C. and more preferably from 70° C. to 130° C.
• the softening point of the polymer is 60° C. or more, bleeding thereof during molding tends to be suppressed, thus improving moldability.
• the softening point thereof is 150° C. or less, compatibility with the epoxy resin and the curing agent tends to be improved.
• Examples of the other aromatic olefin to be copolymerized with acenaphthylene include styrene, ⁇ -methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, or alkyl substitution products thereof.
• aliphatic olefin can be used in combination in a range not impairing the advantageous effects of the present invention.
• Examples of the aliphatic olefin include (meth)acrylic acids and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid, and esters thereof.
• An amount of addition of the aliphatic olefins is preferably 20% by mass or less, and more preferably 9% by mass or less in a total amount of polymerizable monomers used in pre-mixing with the phenol aralkyl resin and the naphthol aralkyl resin.
• Examples of a method that can pre-mix a part or all of the curing agent with acenaphthylene include a method in which the curing agent and acenaphthylene, respectively, are pulverized minutely and mixed together in their solid states by a mixer or the like, a method in which both of the ingredients are evenly dissolved in a solvent for dissolving both thereof and then the solvent is removed, and a method in which both of the ingredients are fused and mixed together at a temperature not less than a softening point of at least one of the curing agent and acenaphthylene.
• the fusing and mixing method is preferable, since an evenly blended mixture can be obtained and impurity mixing is reduced.
• a pre-mixture (an acenaphthylene-modified curing agent) is produced.
• the temperature for the fusion and mixing is not less than a softening point of the at least one of the curing agent and acenaphthylene.
• the temperature is preferably from 100° C. to 250° C., and more preferably from 120° C. to 200° C.
• the time for the fusion and mixing is not particularly limited, but preferably from one hour to 20 hours, and more preferably from two hours to 15 hours.
• dicyclopentadiene phenol resin examples include a phenol resin represented by the following general formula (XXXI).
• R 1 s each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms
• R 2 s each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms
• n represents an integer from 0 to 10
• m represents an integer from 0 to 6.
• substituents in the hydrocarbon groups include a halogen atom, an amino group and a sulfanyl group.
• R 1 in the general formula (XXXXI) include a hydrogen atom; substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a tert-butyl group; alkenyl groups such as a vinyl group, an allyl group and a butenyl group; halogenated alkyl groups, amino group-substituted alkyl groups, and sulfanyl group-substituted alkyl groups.
• alkyl groups such as a methyl group and an ethyl group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable.
• R 2 include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a tert-butyl group, alkenyl groups such as a vinyl group, an allyl group and a butenyl group, and halogenated alkyl groups, amino group-substituted alkyl groups, and sulfanyl group-substituted alkyl groups.
• m represents an integer from 0 to 6, but preferably represents 0.
• Examples of a commercially available product of the dicyclopentadiene phenol resin in which R 1 represents a hydrogen atom and m represents 0 include DPP (trade name, manufactured by Nippon Petrochemicals Co., Ltd).
• the content percentage of the dicyclopentadiene phenol epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in the amount of the entire curing agent in order to allow the resin to exhibit performance thereof.
• novolac phenol resin examples include a novolac phenol resin such as a phenol resin represented by the following general formula (XXXXII) and a cresol novolac resin. Particularly preferred is a novolac phenol resin represented by the following general formula (XXXXII).
• R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; i represents an integer from 0 to 3; and n represents an integer from 0 to 10.
• substituent in the hydrocarbon group include a halogen atom, an amino group and a mercapto group.
• R in the general formula (XXXXII) include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a tert-butyl group, alkenyl groups such as a vinyl group, an allyl groups and a butenyl group, halogenated alkyl groups, amino group-substituted alkyl groups and mercapto group-substituted alkyl groups.
• R represents an alkyl group such as a methyl group or an ethyl group, and more preferably i represents 0.
• n has an average value of from 0 to 8.
• Examples of a commercially available product of the novolac phenol resin represented by the general formula (XXXII) include H-4: trade name, manufactured by Meiwa Plastic Industries Ltd.
• the content percentage of the novolac phenol resin is preferably 30% by mass or more, and more preferably 50% by mass or more, in the amount of the entire curing agent in order to allow the resin to exhibit performance thereof.
• any one of the curing agents may be used alone or two or more thereof may be used in combination.
• the content percentage of the combination in total is preferably 50% by mass or more, more preferably 60% by mass, and 80% by mass or more in the amount of the entire curing agent.
• the hydroxyl group equivalent weight of the curing agent is not particularly limited. Particularly, from the viewpoint of the balance between the various characteristics such as moldability, reflow resistance and electrical reliability, the hydroxyl equivalent weight thereof is preferably from 70 g/eq to 1000 g/eq., and more preferably from 80 g/eq to 500 g/eq.
• the softening point or melting point of the curing agent is not particularly limited, and is, particularly from the viewpoint of moldability and reflow resistance, preferably from 40° C. to 180° C., and from the viewpoint of handleability in the production of the epoxy resin molding material for sealing, more preferably from 50° C. to 130° C.
• an equivalent weight ratio of the epoxy resin (A) to the curing agent (B), namely a ratio of the numbers of hydroxyl groups in the curing agent with respect to epoxy groups (numbers of hydroxyl groups in the curing agent/numbers of epoxy groups in the epoxy resin) is not particularly limited.
• the ratio is set preferably in a range of from 0.5 to 2.0, and more preferably in a range of from 0.6 to 1.3.
• the ratio is set still more preferably in a range of from 0.8 to 1.2.
• the epoxy resin molding material for sealing includes at least one curing accelerator.
• the curing accelerator is not particularly limited as long as the compound is commonly used in epoxy resin molding materials for sealing.
• Examples of the curing accelerator include cycloamidine compounds such as 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonen-5 and 5,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7; compounds having intramolecular polarization obtained by adding, to these cycloamidine compounds, ⁇ bond-containing compounds such as maleic anhydrides, quinone compounds such as 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4 benzoquinone, 2,3-dimethoxy-1,4-benzo
• the curing accelerator is preferably an adduct of a tertiary phosphine and a quinone compound, and more preferably an adduct of triphenylphosphine and benzoquinone or an adduct of tributylphosphine and benzoquinone.
• the curing accelerator is preferably an adduct of a cycloamidine compound and a phenol resin, and more preferably a novolac phenol resin salt of diazabicycloundecene (hereinafter also referred to as “specific curing accelerator”).
• the content percentages of these specific curing accelerators are preferably 60% by mass or more, and more preferably 80% by mass in total in the amount of the entire curing accelerator.
• the tertiary phosphine used in the adduct of a tertiary phosphine and a quinone compound is not particularly limited.
• the tertiary phosphine include tributyl phosphine, and tertiary phosphines having aryl groups such as dibutylphenyl phosphine, butyldiphenyl phosphine, ethyldiphenyl phosphine, triphenyl phosphine, tris(4-methylphenyl) phosphine, tris(4-ethylphenyl) phosphine, tris(4-propylphenyl) phosphine, tris(4-butylphenyl) phosphine, tris(isopropylphenyl) phosphine ,tris(tert-butylphenyl) phosphine, tris(2,4-d
• the quinone compound used in the adduct of a tertiary phosphine and a quinone compound is not particularly limited.
• the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone and anthraquinone. From the viewpoint of moisture resistance or preservation stability, p-benzoquinone is preferable.
• the content percentage of the curing accelerator is not particularly limited as long as the amount of the curing accelerator is an amount capable of achieving curing acceleration effect.
• the content percentage thereof is preferably from 0.1 parts by mass to 10 parts by mass, and more preferably from 0.3 parts by mass to 5 parts by mass, with respect to 100 parts by mass as the total amount of the epoxy resin (A) and the curing agent (B).
• the content percentage thereof is 0.1 parts by mass or more, curing can be achieved in a short time.
• the content percentage thereof is 10 parts by mass or less, excessively fast rate of curing is suppressed, whereby a more favorable molded article tends to be obtained.
• the epoxy resin molding material for sealing includes at least one inorganic filler.
• the inorganic filler By including the inorganic filler, hygroscopicity suppression, reduction in linear expansion coefficient, improvement in thermal conductivity, and strength improvement are more effectively achieved.
• the inorganic filler is not particularly limited as long as the filler is commonly used in epoxy resin molding materials for sealing.
• the inorganic filler examples include powders of fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite and titania, beads obtained by spheroidization of these powders, and glass fibers. Any one of these may be used alone or two or more thereof may be used in combination. Among them, from the viewpoint of reducing linear expansion coefficient, fused silica is preferable. In addition, from the viewpoint of high thermal conductivity, alumina is preferable. Meanwhile, the inorganic filler is preferably spherical in shape, in terms of fluidity and mold abrasiveness during molding.
• the inorganic filler is preferably spherical fused silica, particularly from the viewpoint of a balance between cost and performance.
• the average particle size of the inorganic filler is not particularly limited. Particularly from the viewpoint of moldability, the average particle size is preferably from 5 ⁇ m to 50 ⁇ m, and more preferably from 10 ⁇ m to 30 ⁇ m. Additionally, the average particle size of the inorganic filler is measured as a volume average particle size, using a laser diffraction/scattering grain size distribution measuring apparatus.
• the relative surface area of the inorganic filler is not particularly limited. Particularly from the viewpoint of moldability and strength, the relative surface area thereof is preferably from 0.5 m 2 /g to 12 m 2 /g, and more preferably from 1 m 2 /g to 5 m 2 /g.
• the relative surface area of the inorganic filler is measured based on nitrogen absorption ability at 77K in accordance with JIS Z 8830.
• the content percentage of the inorganic filler is not particularly limited as long as the percentage is in a range capable of achieving the present invention.
• the content percentage thereof is preferably from 70% by mass to 95% by mass in the epoxy resin molding material for sealing, and from the view t ⁇ 002211+:055 ⁇ . . . point of hygroscopicity reduction and reduction in linear expansion coefficient, more preferably from 85% by mass to 95% by mass therein.
• the content percentage of the inorganic filler is 70% by mass or more, flame retardancy and reflow resistance tend to be improved.
• excellent fluidity tends to be obtained.
• the epoxy resin molding material for sealing can include, from the viewpoint of improvement adhesiveness and the like between the resin ingredient and the inorganic ingredient in the molding material, silane compounds other than (E1) the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxysilane compound as needed.
• the other silane compounds include various silane based compounds such as mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane.
• the other silane compounds exclude silane based compounds that overlap (E1) the arylamino group-containing alkoxysilane compound and (E2) the epoxy group-containing alkoxysilane compound.
• silane compounds include unsaturated bond-containing silane compounds such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyl trimethoxysilane, ⁇ -methacryloxypropyl triethoxysilane, ⁇ -methacryloxypropylmethyl dimethoxysilane, ⁇ -methacryloxypropylmethyl diethoxysilane, ⁇ -methacryloxypropyl dimethyl methoxysilane, ⁇ -methacryloxypropyl dimethyl ethoxysilane, ⁇ -acryloxypropyl trimethoxysilane, ⁇ -acryloxypropyl triethoxysilane, and vinyl triacetoxysilane; sulfur atom-containing silane compounds such as ⁇ -mercaptopropyl trimethoxysilane, ⁇ -mercaptopropyl triethoxysi
• the total content percentage thereof is, from the viewpoint of moldability and adhesiveness, preferably from 0.06% by mass to 2% by mass, more preferably from 0.1% by mass to 0.75% by mass, and still more preferably from 0.2% by mass to 0.7% by mass in the epoxy resin molding material for sealing.
• the total content percentage thereof is 0.06% by mass or more, adhesiveness tends to be further improved.
• the total content percentage thereof is 2% by mass or less, the occurrence of molding failure such as voids tends to be able to be suppressed.
• the epoxy resin molding material for sealing may include a conventionally known coupling agent other than the silane compounds, from the viewpoint of improving the adhesiveness between the resin ingredient and the inorganic ingredient in the molding material.
• the coupling agent include titanate based coupling agents such as isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(ditridecyl) phosphite titanate, bis(dioctylpyrophosphate) oxyacetate titanate, bis(dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dim
• the total content percentage thereof is, from the viewpoint of moldability and adhesiveness, preferably from 0.06% by mass to 2% by mass, more preferably from 0.1% by mass to 0.75% by mass, and still more preferably from 0.2% by mass to 0.7% by mass in the epoxy resin molding material for sealing.
• the total content percentage thereof is 0.06% by mass or more, adhesiveness tends to be further improved.
• the total content percentage thereof is 2% by mass or less, the occurrence of molding failures such as voids tends to be able to be suppressed.
• the epoxy resin molding material for sealing can include, as needed, an anion exchanger, from the viewpoint of improving moisture resistance and high temperature exposure characteristics of a sealed device.
• the anion exchanger is not particularly limited and can be a conventionally known one.
• Examples of the conventionally known anion exchanger include hydrotalcites and hydroxides including an element selected from magnesium, aluminium, titanium, zirconium and bismuth. Any one of these may be used alone or two or more thereof may be used in combination. Among them, preferred is a hydrotalcite represented by the following composition formula (XXXXIII).
• X represents a value satisfying 0 ⁇ X ⁇ 0.5 and m represents a positive value.
• the content percentage of the anion exchanger is not particularly limited as long as the amount of the anion exchanger is sufficient to capture anion ions such as halogen ions.
• the content percentage thereof is preferably from 0.1 parts by mass to 30 parts by mass, and more preferably from 1 parts by mass to 5 parts by mass, with respect to 100 parts by mass of the epoxy resin (A).
• the epoxy resin molding material for sealing of the present invention can include an adhesion accelerator as needed, from the viewpoint of further improving adhesiveness.
• the adhesion accelerator include derivatives such as imidazole, triazole, tetrazole, and triazine, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline and the like, and derivatives thereof, aliphatic acid amide compounds, dithiocarbamates, and thiadiazole derivatives. Any one of these may be used alone or two or more thereof may be used in combination.
• the epoxy resin molding material for sealing may include a mold release agent as needed.
• a mold release agent for example, oxidized or nonoxidized polyolefin may be included in an amount of preferably from 0.01 parts by mass to 10 parts by mass, and more preferably from 0.1 parts by mass to 5 parts by mass, with respect to 100 parts by mass of the epoxy resin (A).
• the polyolefin content is 0.01 parts by mass or more, a favorable mold release performance tends to be obtainable.
• the polyolefin content is 10 parts by mass or less, adhesiveness tends to be improved.
• oxidized or nonoxidized polyolefin examples include low molecular weight polyethylenes having a number average molecular weight of from about 500 to 10000, such as H4, PE, and PED series: trade names, manufactured by Hoechst Ltd.
• examples of mold release agents other than the oxidized or nonoxidized polyolefins include carnauba wax, montanoic acid esters, montanoic acid and stearic acid. Any one of these may be used alone or two or more thereof may be used in combination.
• the content thereof is preferably from 0.1 parts by mass to 10 parts by mass, and more preferably from 0.5 parts by mass to 3 parts by mass as a total amount of the mold release agents, with respect to 100 parts by mass of the epoxy resin (A).
• the epoxy resin molding material for sealing can include a conventionally known flame retardant as needed, from the viewpoint of improving the flame retardancy of the molding material.
• the flame retardant include brominated epoxy resin, antimony trioxide, phosphorous compounds such as red phosphorus, red phosphorus coated by inorganic material such as zinc oxide, aluminium hydroxide, magnesium hydroxide and/or a thermosetting resin such as a phenol resin, and phosphate ester, nitrogen-containing compounds such as melamine, melamine derivatives, melamine-modified phenol resins, triazine ring-containing compounds, cyanuric acid derivatives, and isocyanuric acid derivatives, phosphorus- and nitrogen-containing compounds such as cyclophosphazene, metal element-containing compounds such as aluminium hydroxide, magnesium hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron, and a composite metal hydroxide
• M 1 and M 2 represent metal elements different from each other, and a, b, c, d, p, q and m represent positive values.
• M 1 and M 2 in the composition formula (XXXXIV) are not particularly limited as long as the metal elements represented thereby are different from each other.
• M 1 is selected from metal elements of the third period, alkali earth metal elements of Group IIA, and metal elements belonging to Group IVB, Group IIB, Group VIII, Group IB, Group IIIA, and Group IVA
• M 2 is selected from transition metal elements of Groups IIIB to IIB. More preferably, M 1 is selected from magnesium, calcium, aluminium, tin, titanium, iron, cobalt, nickel, copper and zinc, and M 2 is selected from iron, cobalt, nickel, copper and zinc.
• M 1 represents magnesium and M 2 represents zinc or nickel.
• the mole ratio of p to q is not particularly limited. The ratio of p/q is preferably from 1/99 to 1/1. Additionally, a, b, c and d are appropriately selected in accordance with M 1 and M 2 .
• Classification of the metal elements was made based on a long-period periodic table including typical elements as Subgroup A and transition elements as Subgroup B (source: Kagaku Daijiten (Chemical Encyclopedia), 30th, reduced-size edition, Kyoritsu Shuppan, Feb. 15, 1987).
• examples of the flame retardant include metal element-containing compounds such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate and dicyclopentadienyl iron. Any one of these flame retardants may be used alone or two or more thereof may be used in combination.
• the content of the flame retardant is not particularly limited. Particularly, the content thereof is preferably from 1 parts by mass to 30 parts by mass, and more preferably from 2 parts by mass to 15 parts by mass, with respect to 100 parts by mass of the epoxy resin (A).
• the epoxy resin molding material for sealing can include a colorant such as carbon black, an organic dye, an organic pigment, titanium oxide, red lead and colcothar. Furthermore, the material for sealing can include, as other additives, a thermoplastic resin such as a polyphenylene ether and an indene oligomer that is a copolymer resin of an indene such as indene or alkyl indene, a styrene such as styrene or alkyl styrene and a phenol, and a stress relaxation agent such as silicone oil or silicone rubber powder, as needed.
• a thermoplastic resin such as a polyphenylene ether and an indene oligomer that is a copolymer resin of an indene such as indene or alkyl indene, a styrene such as styrene or alkyl styrene and a phenol
• a stress relaxation agent such as silicone oil or silicone rubber powder
• the epoxy resin molding material for sealing can be prepared using any method as long as various ingredients can be evenly dispersed and mixed together.
• predetermined amounts of ingredients to be added are mixed together sufficiently by a mixer or the like, then fused and kneaded by an extruder or the like, and cooled down and pulverized.
• the epoxy resin molding material for sealing can be obtained by evenly stirring and mixing the predetermined amounts of the ingredients described above and then performing kneading with a kneader, a roll, an extruder, or the like preheated to from 70° C. to 140° C., cooling down, pulverizing and the like.
• the obtained material can be made easily usable by making into tablet with a size and a mass so as to meet molding requirements.
• An electronic component device of the present invention includes an element sealed with the epoxy resin molding material for sealing, and is formed by including, as needed, other constituent components.
• the electronic component device including an element sealed with the epoxy resin molding material for sealing include electronic component devices in which elements such as active elements such as a semiconductor chip, transistors, diodes and thyristors, and passive elements such as capacitors, resistors and coils are mounted on a support member such as a lead frame, a wired tape carrier, a wiring board, glass or silicon wafer, and necessary parts are sealed with the epoxy resin molding material for sealing.
• elements such as active elements such as a semiconductor chip, transistors, diodes and thyristors, and passive elements such as capacitors, resistors and coils are mounted on a support member such as a lead frame, a wired tape carrier, a wiring board, glass or silicon wafer, and necessary parts are sealed with the epoxy resin molding material for sealing.
• Examples of such electronic component devices include common resin-sealed ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package), which are formed by fixing a semiconductor element on a lead frame, connecting element terminals such as bonding pads to lead portions by wire bonding or bumps, and then sealing with the epoxy resin molding material for sealing by transfer molding or the like; TCP (Tape Carrier Package) formed by connecting a semiconductor chip to a tape carrier by bumps and sealing the chip with the epoxy resin molding material for sealing; COB (Chip On Board) modules, hybrid ICs, and multichip modules, in which active elements such as semiconductor chips, transistors, diodes and thyristors and/or passive elements such as capacitors, resistors and coils connected to wires formed on a
• a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method or the like may be used.
• conditions for sealing elements can be appropriately selected in accordance with the structure and the like of the epoxy resin molding material for sealing.
• epoxy resin (A) As the epoxy resin (A), the followings were used:
• the inorganic filler (D) As the inorganic filler (D), a spherical fused silica having an average particle size of 17.5 ⁇ m and a relative surface area of 3.8 m 2 /g was used.
• (E1) silane compound 1 As (E1) the arylamino group-containing alkoxysilane compound, ⁇ -anilinopropyl trimethoxysilane ((E1) silane compound 1) was used.
• ⁇ -aminopropyl trimethoxysilane (the other silane compound 1) was used.
• carnauba wax (Clariant Japan Co., Ltd.), antimony trioxide, and carbon black (Mitsubishi Chemical Co. Ltd) were used.
• the each epoxy resin molding material for sealing was molded into a disk with a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after the molding, hot hardness was measured using a Shore Type D hardness tester (HD-1120 (TYPE D) manufactured by Ueshima Seisakusho Co., Ltd).
• the epoxy resin molding materials for sealing were molded into a shape of 10 mm ⁇ 70 mm ⁇ 3 mm under the above conditions and then post-curing was performed to produce test pieces.
• a three-point supported bending test in accordance with JIS-K-6911 was performed in a thermostat chamber maintained at 260° C. using TENSILON manufactured by A&D Co., Ltd., to obtain a bending elastic modulus (MPa) at 260° C.
• the disks molded in the (2) were post-cured under the above conditions.
• the obtained disks were allowed to stand for 168 hours under conditions of 85° C. and 60% RH to measure changes in mass before and after allowing to stand, and then evaluation was performed using an equation:
• a 80 pin flat package (lead frame material: copper alloy; die pad upper surface and lead tip: silver-plated) having outline dimensions of 20 mm ⁇ 14 mm ⁇ 2 mm, which mounts a silicon chip having dimensions of 8 mm ⁇ 10 mm ⁇ 0.4 mm, was produced by molding and post-curing each of the epoxy resin molding materials for sealing under the above conditions.
• the obtained each package was humidified for 168 hours under conditions of 85° C. and 85% RH, and then subjected to reflow treatment under conditions of predetermined temperatures (235° C., 245° C. and 255° C.) and 10 seconds.
• Tables 1 to 6 indicate that Comparative Examples 1 to 13 in which the compounds of the ingredients (E1) and (E2) were not added in combination were inferior in terms of fluidity and reflow resistance. Comparative Examples 3, 5, 8 and 11 including only the compound of the ingredient (E1) are inferior in terms of reflow resistance, and Comparative Examples 1, 2, 4, 6, 7, 9, 10, 12 and 14 including only the compound of the ingredient (E2) are inferior in terms of fluidity and reflow resistance. In addition, in Comparative Example 13 including an amino group-containing silane compound having a different structure from the ingredient (E1), fluidity and reflow resistance were significantly reduced, and also were inferior in terms of flame retardancy, thus not achieving UL-94 V-0.
• Examples 1 to 24 including the combination of the ingredients (E1) and (E2) as compared with Comparative Examples having the same resin composition except that the formulation of the silane compounds other than the ingredients (E1) and (E2) was partially different, excellent reflow resistance and excellent moldabilities such as fluidity and hot hardness were obtained, as well as all of the Examples achieved UL-94 V-0 and also had excellent flame retardancy.

Landscapes

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

Applications Claiming Priority (5)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=47176853

Family Applications (2)

Family Applications After (1)

Country Status (6)

Cited By (3)

Families Citing this family (13)

Citations (2)

Family Cites Families (26)

• 2012
  • 2012-05-10 KR KR1020187025941A patent/KR20180104168A/ko not_active Application Discontinuation
  • 2012-05-10 CN CN201510815340.4A patent/CN105440582A/zh active Pending
  • 2012-05-10 CN CN201910098035.6A patent/CN109971122A/zh active Pending
  • 2012-05-10 WO PCT/JP2012/062063 patent/WO2012157529A1/ja active Application Filing
  • 2012-05-10 JP JP2013515110A patent/JPWO2012157529A1/ja active Pending
  • 2012-05-10 KR KR1020137032049A patent/KR101899186B1/ko active IP Right Grant
  • 2012-05-10 CN CN201280023016.3A patent/CN103517948A/zh active Pending
  • 2012-05-10 US US14/116,979 patent/US20140128505A1/en not_active Abandoned
  • 2012-05-11 TW TW108101601A patent/TW201938680A/zh unknown
  • 2012-05-11 TW TW101116850A patent/TWI647275B/zh active
  • 2012-05-11 TW TW106101518A patent/TWI670319B/zh active
• 2016
  • 2016-02-03 JP JP2016019261A patent/JP6304271B2/ja active Active
  • 2016-08-23 JP JP2016162942A patent/JP6478953B2/ja active Active
• 2017
  • 2017-01-12 US US15/404,224 patent/US10662315B2/en active Active
  • 2017-09-13 JP JP2017175952A patent/JP6753378B2/ja active Active

Patent Citations (2)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events