TWI628229B - Film forming resin composition, insulating film and semiconductor device - Google Patents

Film forming resin composition, insulating film and semiconductor device Download PDF

Info

Publication number
TWI628229B
TWI628229B TW103133904A TW103133904A TWI628229B TW I628229 B TWI628229 B TW I628229B TW 103133904 A TW103133904 A TW 103133904A TW 103133904 A TW103133904 A TW 103133904A TW I628229 B TWI628229 B TW I628229B
Authority
TW
Taiwan
Prior art keywords
component
resin composition
parts
mass
film
Prior art date
Application number
TW103133904A
Other languages
Chinese (zh)
Other versions
TW201516088A (en
Inventor
高杉寛史
戸島順
寺木慎
Original Assignee
納美仕有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 納美仕有限公司 filed Critical 納美仕有限公司
Publication of TW201516088A publication Critical patent/TW201516088A/en
Application granted granted Critical
Publication of TWI628229B publication Critical patent/TWI628229B/en

Links

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08K3/10—Metal 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/29294—Material of the matrix with a principal constituent of the material being a liquid not provided for in groups H01L2224/292 - H01L2224/29291
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/29386—Base material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/2939—Base material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/2939—Base material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H01L2224/29391—The principal constituent being an elastomer, e.g. silicones, isoprene, neoprene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/29393—Base material with a principal constituent of the material being a solid not provided for in groups H01L2224/293 - H01L2224/29391, e.g. allotropes of carbon, fullerene, graphite, carbon-nanotubes, diamond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

本發明之目的係提供一種薄膜用樹脂組成物，其絕緣性、耐熱性優異，且填入絕緣填料仍可維持接著強度，特別是，即使高度填入高導熱性填料亦可維持接著強度者。 The object of the present invention is to provide a resin composition for a film, which is excellent in insulation and heat resistance, and can maintain the adhesive strength when filled with an insulating filler. In particular, it can maintain the adhesive strength even when a highly thermally conductive filler is filled.

本發明之薄膜用樹脂組成物，其特徵係：包含下述(A)、(B)、(C)、(D)與(E)成分，且相對於(A)成分、(B)成分、(C)成分及(D)成分之總和100質量份，(C)成分為0.5至30.0質量份，(A)在兩末端具有與特定乙烯基鍵結的苯基之聚醚化合物、(B)熱塑性彈性體、(C)萘型環氧樹脂、(D)硬化劑、(E)絕緣填料。 The resin composition for a film of the present invention is characterized in that it contains the following components (A), (B), (C), (D), and (E), and is compared with the components (A), (B), and 100 parts by mass of the total of the component (C) and the component (D), the component (C) is 0.5 to 30.0 parts by mass, (A) a polyether compound having a phenyl group bonded to a specific vinyl group at both ends, and (B) Thermoplastic elastomer, (C) naphthalene-type epoxy resin, (D) hardener, (E) insulating filler.

Description

薄膜用樹脂組成物、絕緣膜及半導體裝置 Thin film resin composition, insulating film and semiconductor device

本發明係有關薄膜用樹脂組成物、由該薄膜用樹脂組成物所形成之絕緣膜及包含該絕緣膜硬化物的半導體裝置。 The present invention relates to a resin composition for a thin film, an insulating film formed from the resin composition for a thin film, and a semiconductor device including the cured product of the insulating film.

近年來，隨著模組與電子零件之高功能化及高密度化，由模組與電子零件等發熱體所產生的熱量持續增大。來自該等發熱體之熱係傳送到基板等而散熱。為了有效地進行該導熱，在發熱體與基板之間的接著劑係使用高導熱率者。並且，從方便操作之觀點，接著劑係以高導熱之接著膜取代。 In recent years, with the higher functionality and higher density of modules and electronic parts, the heat generated by heating elements such as modules and electronic parts has continued to increase. The heat from these heating elements is transmitted to a substrate or the like and is radiated. In order to perform this thermal conduction efficiently, a high thermal conductivity is used as the adhesive between the heating element and the substrate. In addition, from the viewpoint of ease of handling, the adhesive is replaced with a highly thermally conductive adhesive film.

其中，如接著膜之導熱不佳，則熱量積聚在組入有模組與電子零件之半導體裝置中，會有引發半導體裝置故障之問題。因此，各企業已在進行高導熱率之接著膜的開發。 Among them, if the thermal conductivity of the subsequent film is not good, heat is accumulated in the semiconductor device incorporating the module and the electronic component, which may cause the failure of the semiconductor device. Therefore, various companies have been developing adhesive films with high thermal conductivity.

對上述接著膜，不僅要求導熱性，亦有絕緣性、耐熱性及連接可靠性(接著強度)之需求。在導熱性方面，如使接著膜含有大量的高導熱性填料雖可提高導熱 性，但隨著填料填量的增加，相對的減少接著膜中之樹脂成分之量，故有難以賦予接著膜所需要的接著強度之問題。而且，此種隨著該填料填量的增加而降低接著膜之接著強度的問題，並不僅限於高導熱之接著膜，例如，從低熱膨脹率化之觀點，在組成物中填入填料時亦會產生此種問題。 The above-mentioned adhesive film requires not only thermal conductivity, but also insulation, heat resistance, and connection reliability (adhesive strength). In terms of thermal conductivity, if the adhesive film contains a large amount of highly thermally conductive filler, the thermal conductivity can be improved. However, with the increase of the filler filling amount, the amount of the resin component in the adhesive film is relatively decreased, so that it is difficult to provide the adhesive strength required for the adhesive film. In addition, such a problem that the adhesive strength of the adhesive film is decreased as the filler amount increases is not limited to adhesive films with high thermal conductivity. For example, from the viewpoint of lowering the thermal expansion coefficient, the filler is also filled into the composition. Such problems can arise.

而且，對於耐熱性，在傳統摻入填料之接著膜的樹脂主成分之丙烯酸樹脂或環氧樹脂亦期望使用耐高熱之樹脂成分。 Further, for heat resistance, it is also desirable to use a resin component having a high heat resistance in an acrylic resin or an epoxy resin, which is a resin main component of a conventional adhesive film in which a filler is incorporated.

其中，專利文獻1揭示一種環氧樹脂，其係應用在薄膜成形、塗佈等步驟中具有充分的成膜性及延展性，且導熱性、耐熱性及可撓性等各種物性亦為優異之具有聯苯骨架的環氧樹脂；專利文獻2中揭示一種環氧樹脂，儘管係導入介晶基團，亦容易製造，且在有機溶劑中之溶解性優異，可賦予強韌性、導熱性優異之硬化物者。 Among them, Patent Document 1 discloses an epoxy resin, which has sufficient film-forming properties and ductility in steps such as film forming and coating, and has various physical properties such as thermal conductivity, heat resistance, and flexibility. An epoxy resin having a biphenyl skeleton; Patent Document 2 discloses an epoxy resin that is easy to manufacture despite the introduction of mesogenic groups, and has excellent solubility in organic solvents, and can impart strong toughness and excellent thermal conductivity. Hardened person.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2012-107215號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2012-107215

[專利文獻2]日本特開2010-001427號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2010-001427

然而，上述具有聯苯骨架之環氧樹脂(專利文獻1)及導入介晶基團之環氧樹脂(專利文獻2)係在填入 填料時，都會有接著強度不足之問題。 However, the above-mentioned epoxy resin having a biphenyl skeleton (Patent Document 1) and an epoxy resin having a mesogenic group (Patent Document 2) are filled in When filling, there is a problem of insufficient bonding strength.

本發明係因鑑於上述情形而完成者，其目的係提供一種絕緣性、耐熱性優異，且即使填入填料亦可維持接著強度的薄膜用樹脂組成物，特別是，即使高度填入高導熱性之填料亦可維持接著強度的薄膜用樹脂組成物。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition for a thin film which is excellent in insulation and heat resistance and maintains adhesive strength even when filled with a filler. In particular, it has high thermal conductivity even when highly filled. The filler may also maintain the adhesive strength of the film resin composition.

本發明係有關藉由具有下述構成而解決上述問題之薄膜用樹脂組成物、絕緣膜及半導體裝置。 The present invention relates to a resin composition for a thin film, an insulating film, and a semiconductor device which have the following constitutions to solve the above problems.

[1]一種薄膜用樹脂組成物，其特徵係：包含下述(A)、(B)、(C)、(D)與(E)，且相對於(A)成分、(B)成分、(C)成分及(D)成分之總和100質量份，(C)成分為0.5至30.0質量份，(A)以下通式(1)所示之兩末端至少具有鍵結有乙烯基的苯基之聚醚化合物、(B)熱塑性彈性體、(C)萘型環氧樹脂、(D)硬化劑、(E)絕緣填料， [1] A resin composition for a film, which is characterized by including the following (A), (B), (C), (D), and (E) with respect to the components (A), (B), and 100 parts by mass of the total of the component (C) and the component (D), the component (C) is 0.5 to 30.0 parts by mass, and (A) the phenyl group having at least vinyl groups bonded to both ends shown by the following general formula (1) Polyether compound, (B) thermoplastic elastomer, (C) naphthalene-type epoxy resin, (D) hardener, (E) insulating filler,

(式中，R1、R2、R3、R4、R5、R6及R7可相同或相異，係氫原子、鹵原子、烷基、鹵烷基或苯基；-(O-X-O)-係以構造式(2)表示，其中，R8、R9、R10、R14及R15可相同或相異，係鹵原子或碳數6以下之烷基或苯基，R11、R12及R13可相同或相異，係氫原子、鹵原子、或碳數6以下之烷基或苯基；-(Y-O)-係構造式(3)所示之1種構造、或構造式(3)所示之2種以上之構造經隨機排列者，其中，R16及R17可相同或相異，係鹵原子或碳數6以下之烷基或苯基，R18及R19可相同或相異，係氫原子、鹵原子或碳數6以下之烷基或苯基；Z為碳數1以上之有機基，視情況亦包含氧原子、氮原子、硫原子及鹵原子；a、b之至少一者不為0，表示0至300之整數；c、d表示0或1之整數)。 (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different, and are hydrogen atom, halogen atom, alkyl group, haloalkyl group or phenyl group;-(OXO )-Is represented by structural formula (2), wherein R 8 , R 9 , R 10 , R 14, and R 15 may be the same or different, and are a halogen atom or an alkyl group or a phenyl group having 6 or less carbon atoms, and R 11 , R 12 and R 13 may be the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group or a phenyl group having a carbon number of 6 or less;-(YO)-is a structure represented by structural formula (3), or Those in which two or more kinds of structures represented by the structural formula (3) are randomly arranged, wherein R 16 and R 17 may be the same or different, and are halogen atoms or alkyl groups or phenyl groups having a carbon number of 6 or less, R 18 and R 19 may be the same or different, being a hydrogen atom, a halogen atom, or an alkyl group or a phenyl group having a carbon number of 6 or less; Z is an organic group having a carbon number of 1 or more, and optionally includes an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom ; At least one of a and b is not 0, which represents an integer from 0 to 300; c, d represents an integer of 0 or 1).

[2]如上述[1]所述之薄膜用樹脂組成物，其中，(E)成分係 選自MgO、Al2O3、AlN、BN、鑽石填料、ZnO及SiC所成組群中之至少1種。 [2] The resin composition for a film according to the above [1], wherein the component (E) is at least one selected from the group consisting of MgO, Al 2 O 3 , AlN, BN, diamond filler, ZnO, and SiC. 1 species.

[3]如上述[1]或[2]所述之薄膜用樹脂組成物，其中，硬化後之薄膜用樹脂組成物之體積電阻率為1×1010Ω．cm以上。 [3] The resin composition for a film according to the above [1] or [2], wherein the volume resistivity of the resin composition for a film after curing is 1 × 10 10 Ω. cm or more.

[4]如上述[1]至[3]中任一者所述之薄膜用樹脂組成物，其中，相對於薄膜用樹脂組成物100質量份，E成分為40至95質量份。 [4] The resin composition for a film according to any one of the above [1] to [3], wherein the E component is 40 to 95 parts by mass based on 100 parts by mass of the resin composition for a film.

[5]一種絕緣膜，係由上述[1]至[4]中任一者所述之薄膜用樹脂組成物所形成。 [5] An insulating film formed from the resin composition for a thin film according to any one of the above [1] to [4].

[6]一種半導體裝置，其包含上述[5]所述之絕緣膜的硬化物。 [6] A semiconductor device including the cured product of the insulating film according to the above [5].

依據本發明[1]，可提供一種薄膜用樹脂組成物，其係藉由使用絕緣性、耐熱性優異之(A)成分與改善接著性之(C)成分，而使絕緣性、耐熱性優異，且即使填入(E)絕緣填料亦可維持接著強度者。 According to the present invention [1], it is possible to provide a resin composition for a film, which is excellent in insulation and heat resistance by using the component (A) having excellent insulation and heat resistance and the component (C) having improved adhesion. And, even if it is filled with (E) insulating filler, it can maintain the bonding strength.

依據本發明[5]，可提供一種絕緣膜，其係絕緣性、耐熱性優異，且即使填入(E)絕緣填料亦可維持接著強度者。 According to the present invention [5], it is possible to provide an insulating film that is excellent in insulation and heat resistance, and can maintain the adhesion strength even when the (E) insulating filler is filled.

依據本發明[6]，可提供一種可靠性高的半導體裝置，其係包含絕緣性、耐熱性優異，且即使填入(E)絕緣填料亦可維持接著強度之絕緣膜的硬化物。 According to the present invention [6], it is possible to provide a highly reliable semiconductor device that includes a cured product of an insulating film that is excellent in insulation and heat resistance and can maintain adhesive strength even when the (E) insulating filler is filled.

[薄膜用樹脂組成物] [Resin composition for film]

本發明之薄膜用樹脂組成物，其特徵係：包含下述(A)、(B)、(C)、(D)與(E)，且相對於(A)成分、(B)成分、(C)成分及(D)成分之總和100質量份，(C)成分為0.5至30.0質量份，(A)以下通式(1)所示之兩末端至少具有鍵結有乙烯基的苯基之聚醚化合物、(B)熱塑性彈性體、(C)萘型環氧樹脂、(D)硬化劑、(E)絕緣填料， The resin composition for a film of the present invention is characterized in that it contains the following (A), (B), (C), (D), and (E), with respect to the components (A), (B), and ( C) 100 parts by mass of the total of the component (D), 0.5 to 30.0 parts by mass of the (C) component, (A) the following formula (1) has at least two phenyl groups bonded to a vinyl group at both ends Polyether compound, (B) thermoplastic elastomer, (C) naphthalene-type epoxy resin, (D) hardener, (E) insulating filler,

(式中，R1、R2、R3、R4、R5、R6及R7可相同或相異，係氫原子、鹵原子、烷基、鹵烷基或苯基；-(O-X-O)-係以構造式(2)表示，其中，R8、R9、R10、R14及R15可相同或相異，係鹵原子或碳數6以下之烷基或苯基，R11、R12及R13可相同或相異，係氫原子、鹵原子、或碳數6以下之烷基或苯基；-(Y-O)-係構造式(3)所示之1種構造、或構造式(3)所示之2種以上之構造經隨機排列者，其中，R16及R17可相同或相異，係鹵原子或碳數6以下之烷基或苯基，R18及R19可相同或相異，係氫原子、鹵原子或碳數6以下之烷基或苯基；Z為碳數1以上之有機基，有時還包含氧原子、氮原子、硫原子及鹵原子；a、b之至少一者不為0，表示0至300之整數；c、d表示0或1之整數)。 (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different, and are hydrogen atom, halogen atom, alkyl group, haloalkyl group or phenyl group;-(OXO )-Is represented by structural formula (2), wherein R 8 , R 9 , R 10 , R 14, and R 15 may be the same or different, and are a halogen atom or an alkyl group or a phenyl group having 6 or less carbon atoms, and R 11 , R 12 and R 13 may be the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group or a phenyl group having a carbon number of 6 or less;-(YO)-is a structure represented by structural formula (3), or Those in which two or more kinds of structures represented by the structural formula (3) are randomly arranged, wherein R 16 and R 17 may be the same or different, and are halogen atoms or alkyl groups or phenyl groups having a carbon number of 6 or less, R 18 and R 19 may be the same or different, and is a hydrogen atom, a halogen atom, or an alkyl group or a phenyl group having a carbon number of 6 or less; Z is an organic group having a carbon number of 1 or more, and sometimes includes an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom ; At least one of a and b is not 0, which represents an integer from 0 to 300; c, d represents an integer of 0 or 1).

(A)成分係通式(1)所示之兩末端至少具有鍵結有乙烯基的苯基之聚醚化合物(以下稱為改質OPE)。本發明中，由於使用改質OPE作為熱硬化性樹脂，因此相較於使用以環氧基為主之傳統產品，硬化物之Tg高至216℃，耐熱性優異，且硬化後之薄膜用樹脂組成物不易發生經時變化，可維持半導體裝置的長期可靠性。更且，由於樹脂中親水基之數目少而有吸濕性優異之特徵。因此，即使在接近150℃之溫度使用，硬化後之薄膜用樹脂組成物 亦不會產生剝離，可提供可靠性高的半導體裝置。另外，藉由改質OPE與(B)熱塑性彈性體之效果，硬化後之薄膜用樹脂組成物具有可緩和來自外部的應力之適度柔軟性，因此可緩和半導體裝置內所產生的應力。並且，改質OPE之絕緣性優異，即使由薄膜用樹脂組成物所形成之絕緣膜的厚度變薄，亦可維持半導體裝置之可靠性。該改質OPE係如日本特開2004-59644號公報所記載者。而且，使用高Tg之環氧樹脂的組成物無法成形為膜狀，而使用低Tg之環氧樹脂的組成物雖可成形為膜狀，惟由於所得薄膜之Tg變低，故薄膜之耐熱性變差。然而，由於含有改質OPE之薄膜用樹脂組成物的接著強度降低，因此，本發明中，藉由將改質OPE與作為(C)成分之萘型環氧樹脂組合，而可改善薄膜用樹脂組成物的接著強度。 The component (A) is a polyether compound (hereinafter referred to as modified OPE) having at least both ends of a phenyl group having a vinyl group bonded thereto represented by the general formula (1). In the present invention, since modified OPE is used as the thermosetting resin, the Tg of the cured product is as high as 216 ° C, the heat resistance is excellent, and the cured film resin is compared with the traditional product mainly containing epoxy groups. The composition is less prone to change with time, and the long-term reliability of the semiconductor device can be maintained. Furthermore, since the number of hydrophilic groups in the resin is small, it is characterized by excellent hygroscopicity. Therefore, even when used at temperatures close to 150 ° C, the resin composition for thin films after curing No peeling occurs, and a highly reliable semiconductor device can be provided. In addition, due to the effects of the modified OPE and the (B) thermoplastic elastomer, the cured resin composition for films has moderate flexibility that can alleviate stress from the outside, and thus can reduce stress generated in the semiconductor device. In addition, the modified OPE has excellent insulation properties, and the reliability of the semiconductor device can be maintained even if the thickness of the insulating film formed from the thin film resin composition is reduced. This modified OPE is described in Japanese Patent Application Laid-Open No. 2004-59644. In addition, a composition using an epoxy resin with a high Tg cannot be formed into a film shape, while a composition using an epoxy resin with a low Tg can be formed into a film shape, but the Tg of the obtained film becomes low, so the film has heat resistance Worse. However, since the bonding strength of the resin composition for a film containing modified OPE is reduced, in the present invention, the resin for a film can be improved by combining the modified OPE with a naphthalene-type epoxy resin as the component (C). Adhesive strength of the composition.

於通式(1)所示之改質OPE的-(O-X-O)-之構造式(2)中，R8、R9、R10、R14及R15係以碳數3以下之烷基為佳，R11、R12及R13係以氫原子或碳數3以下之烷基為佳。具體上係可列舉構造式(4)。 In the structural formula (2) of-(OXO)-, which is a modified OPE represented by the general formula (1), R 8 , R 9 , R 10 , R 14, and R 15 are each an alkyl group having a carbon number of 3 or less. Preferably, R 11 , R 12 and R 13 are each a hydrogen atom or an alkyl group having 3 or less carbon atoms. Specific examples include Structural Formula (4).

於-(Y-O)-之構造式(3)中，R16及R17係以碳數3以下之烷基為佳，R18及R19係以氫原子或碳數3以下 之烷基為佳。具體上係可列舉構造式(5)或(6)。 In the structural formula (3) of-(YO)-, R 16 and R 17 are preferably alkyl groups having 3 or less carbon atoms, and R 18 and R 19 are preferably hydrogen atoms or alkyl groups having 3 or less carbon atoms. . Specific examples include structural formula (5) or (6).

Z可列舉如碳數3以下之伸烷基，具體上為亞甲基。 Examples of Z include an alkylene group having a carbon number of 3 or less, and specifically methylene.

a、b之至少一者不為0，表示0至300之整數，以0至30之整數為佳。 At least one of a and b is not 0, which means an integer from 0 to 300, and an integer from 0 to 30 is preferred.

通式(1)之改質OPE係以數量平均分子量1000至4500者為佳。更佳之數量平均分子量為1000至3000。數量平均分子量係藉由凝膠滲透層析法(GPC)，使用標準聚苯乙烯的校正曲線所得之值。 The modified OPE of the general formula (1) is preferably a number average molecular weight of 1,000 to 4500. A more preferred number average molecular weight is 1000 to 3000. The number average molecular weight is a value obtained by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene.

上述改質OPE可單獨使用，亦可將2種以上組合使用。 The modified OPE can be used alone or in combination of two or more.

(B)成分係為了膜成形性而使用。並且，由於(B)成分係使硬化後之薄膜用樹脂組成物具有可緩和來自外部的應力之適度柔軟性，因此可緩和半導體裝置內所產生的應力。(B)成分係可列舉如：苯乙烯-丁二烯嵌段共聚物(SBS)、苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、聚丁二烯(PB)、苯乙烯-(乙烯-乙烯/丙烯)-苯乙烯嵌段共聚物(SEEPS)。(B) 成分可單獨使用，亦可2種以上併用。該等之中，任一者之採用係視其所賦予接著膜之特性而可適當地選擇。例如：從對硬化後之接著膜賦予耐熱性之觀點，係以苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物為佳；從對接著膜賦予接著強度之觀點，係以苯乙烯-(乙烯-乙烯/丙烯)-苯乙烯嵌段共聚物為佳。因此，作為(B)成分，係以併用苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物與苯乙烯-(乙烯-乙烯/丙烯)-苯乙烯嵌段共聚物者為特佳。(B)成分係以重量平均分子量30,000至200,000者為佳。重量平均分子量係藉由凝膠滲透層析法(GPC)，使用標準聚苯乙烯的校正曲線所得之值。 The (B) component is used for film moldability. In addition, since the component (B) provides the resin composition for a thin film after curing with a moderate flexibility that can relieve stress from the outside, the stress generated in the semiconductor device can be relaxed. (B) The component system is exemplified by styrene-butadiene block copolymer (SBS), styrene-ethylene / butene-styrene block copolymer (SEBS), and styrene-isoprene-benzene Ethylene block copolymer (SIS), polybutadiene (PB), styrene- (ethylene-ethylene / propylene) -styrene block copolymer (SEEPS). (B) The ingredients may be used alone or in combination of two or more. Among them, the use of any one can be appropriately selected depending on the characteristics given to the adhesive film. For example, from the viewpoint of imparting heat resistance to the cured adhesive film, styrene-ethylene / butene-styrene block copolymer is preferred; from the viewpoint of imparting adhesive strength to the adhesive film, styrene- ( Ethylene-ethylene / propylene) -styrene block copolymers are preferred. Therefore, it is particularly preferable that the component (B) is a combination of a styrene-ethylene / butene-styrene block copolymer and a styrene- (ethylene-ethylene / propylene) -styrene block copolymer. The component (B) preferably has a weight average molecular weight of 30,000 to 200,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene.

由於(C)成分係改善薄膜用樹脂組成物之接著強度(剝離強度)，故可增加薄膜用樹脂組成物中(E)絕緣填料之填充量。作為(C)成分之萘型環氧樹脂係具有1分子內至少包含1個以上之萘環骨架之環氧樹脂，可列舉如：萘酚系、萘二醇系等。萘型環氧樹脂之例可列舉如：1,3-二縮水甘油醚萘、1,4-二縮水甘油醚萘、1,5-二縮水甘油醚萘、1,6-二縮水甘油醚萘、2,6-二縮水甘油醚萘、2,7-二縮水甘油醚萘、1,3-二縮水甘油酯萘、1,4-二縮水甘油酯萘、1,5-二縮水甘油酯萘、1,6-二縮水甘油酯萘、2,6-二縮水甘油酯萘、2,7-二縮水甘油酯萘、1,3-四縮水甘油胺萘、1,4-四縮水甘油胺萘、1,5-四縮水甘油胺萘、1,6-四縮水甘油胺萘、1,8-四縮水甘油胺萘、2,6-四縮水甘油胺萘、2,7-四縮水甘油胺萘等萘型環氧樹脂。(C)成分，只要為包含上述萘型環氧樹脂者即可，可單獨使用，亦可2種以上併用。特 別是，液狀之2官能萘型環氧樹脂就其為低黏度之點而佳。通過萘型環氧樹脂之使用，改善接著強度(剝離強度)，可增加填料之填充量。其結果，可使接著膜高導熱化。並且，萘型環氧樹脂之耐熱性亦為優異，由於此點，亦可應用在高導熱之用途上。 Since the component (C) improves the adhesion strength (peel strength) of the resin composition for a film, the filling amount of the (E) insulating filler in the resin composition for a film can be increased. The naphthalene-type epoxy resin as the component (C) is an epoxy resin having at least one naphthalene ring skeleton in one molecule, and examples thereof include naphthol-based and naphthalenediol-based. Examples of naphthalene-type epoxy resins include 1,3-diglycidyl ether naphthalene, 1,4-diglycidyl ether naphthalene, 1,5-diglycidyl ether naphthalene, and 1,6-diglycidyl ether naphthalene. , 2,6-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, 1,3-diglycidyl naphthalene, 1,4-diglycidyl naphthalene, 1,5-diglycidyl naphthalene , 1,6-diglycidyl naphthalene, 2,6-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, 1,3-tetraglycidyl naphthalene, 1,4-tetraglycidyl naphthalene , 1,5-tetraglycidylnaphthalene, 1,6-tetraglycidylnaphthalene, 1,8-tetraglycidylnaphthalene, 2,6-tetraglycidylnaphthalene, 2,7-tetraglycidylnaphthalene And other naphthalene type epoxy resin. (C) As long as it is a component containing the said naphthalene type epoxy resin, it may be used individually, and may use 2 or more types together. special In addition, the liquid bifunctional naphthalene-type epoxy resin is preferable because it has a low viscosity. By using a naphthalene-type epoxy resin, the adhesion strength (peel strength) is improved, and the filling amount of the filler can be increased. As a result, the thermal conductivity of the adhesive film can be increased. In addition, the naphthalene-type epoxy resin is also excellent in heat resistance. Because of this, it can also be used in applications with high thermal conductivity.

(D)成分係可列舉如：酚系硬化劑、胺系硬化劑、咪唑系硬化劑及酸酐系硬化劑等。尤其是，從對(C)成分之硬化性、接著性之觀點，(D)成分以咪唑系硬化劑者為佳。 Examples of the component system include a phenol-based hardener, an amine-based hardener, an imidazole-based hardener, and an acid anhydride-based hardener. In particular, from the viewpoint of curability and adhesiveness to the component (C), an imidazole-based hardener is preferred as the component (D).

(E)成分方面，從維持絕緣性之觀點，可使用一般的無機填料。(E)成分方面係以導熱率為5W/m‧K以上者為佳。從絕緣性及熱膨脹係數之觀點，如為選自MgO、Al2O3、AlN、BN、鑽石填料、ZnO、SiC及SiO2所成組群中之至少1種以上的無機填料則佳。從導熱率、絕緣性及熱膨脹係數之觀點，如為選自MgO、Al2O3、AlN、BN、鑽石填料、ZnO及SiC所成組群中之至少1種以上的無機填料則佳。而且，ZnO及SiC中，可因應必要施行絕緣處理。各材料之導熱率的測定結果之一例(單位為W/m‧K)係MgO為37、Al2O3為30、AlN為200、BN為30、鑽石為2000、ZnO為54以及SiC為90。另外，SiO2之導熱率的測定結果之一例(單位為W/m‧K)係1.4。 In the component (E), a general inorganic filler can be used from the viewpoint of maintaining insulation properties. The (E) component is preferably one having a thermal conductivity of 5 W / m · K or more. From the viewpoint of insulation and thermal expansion coefficient, it is preferable to use at least one or more inorganic fillers selected from the group consisting of MgO, Al 2 O 3 , AlN, BN, diamond fillers, ZnO, SiC, and SiO 2 . From the viewpoints of thermal conductivity, insulation, and thermal expansion coefficient, it is preferable to use at least one or more inorganic fillers selected from the group consisting of MgO, Al 2 O 3 , AlN, BN, diamond fillers, ZnO, and SiC. In addition, ZnO and SiC may be subjected to insulation treatment as necessary. An example of the measurement results of the thermal conductivity of each material (unit: W / m‧K) is MgO 37, Al 2 O 3 30, AlN 200, BN 30, diamond 2000, ZnO 54 and SiC 90 . An example of the measurement result of the thermal conductivity of SiO 2 (unit: W / m · K) is 1.4.

(E)成分之平均粒徑(不為粒狀時，其平均最大直俓)並無特別限定，惟以0.05至50μm者，因在薄膜用樹脂組成物中可均勻地分散(E)成分而佳。未達0.05μm 時，薄膜用樹脂組成物之黏度上昇而有成形性變差之虞。超出50μm時，則(E)成分恐難以均勻地分散在由薄膜用樹脂組成物所形成之絕緣膜中。此處，(E)成分之平均粒徑係由動態光散射型納米軌道粒度分析儀測定。(E)成分可單獨使用，亦可2種以上併用。 The average particle diameter of the (E) component (when it is not granular, its average maximum straight diameter) is not particularly limited, but if it is 0.05 to 50 μm, the (E) component can be uniformly dispersed in the resin composition for films. good. Less than 0.05μm In this case, the viscosity of the resin composition for a film may increase and the moldability may deteriorate. If it exceeds 50 μm, it may be difficult for the (E) component to be uniformly dispersed in the insulating film formed of the resin composition for a thin film. Here, the average particle diameter of the (E) component is measured with a dynamic light scattering type nano-orbit particle size analyzer. (E) A component may be used individually or in combination of 2 or more types.

從硬化後之絕緣膜的導熱率及耐熱性之觀點，相對於(A)成分、(B)成分、(C)成分及(D)成分之總和(以下稱為「(A)至(D)成分之總和」)100質量份，(A)成分係以10至60質量份為佳。 From the viewpoint of the thermal conductivity and heat resistance of the cured insulating film, it is relative to the sum of the components (A), (B), (C), and (D) (hereinafter referred to as "(A) to (D) The sum of the components ") is 100 parts by mass, and the component (A) is preferably 10 to 60 parts by mass.

從絕緣膜之成形性及硬化後之絕緣膜的彈性模量之觀點，相對於(A)至(D)成分之總和100質量份，(B)成分係以10至60質量份為佳。 From the viewpoint of the moldability of the insulating film and the elastic modulus of the cured insulating film, the component (B) is preferably 10 to 60 parts by mass relative to 100 parts by mass of the total of the components (A) to (D).

相對於(A)至(D)成分之總和100質量份，(C)成分為0.5至30質量份，以1.0至15質量份為佳。相對於(A)至(D)成分之總和100質量份，(C)成分未達0.5質量份時，無法得到密著性之效果，超出30質量份時，則薄膜單體的耐折性(彎折性)消失而薄膜無法成形。 The component (C) is 0.5 to 30 parts by mass, and preferably 1.0 to 15 parts by mass, with respect to 100 parts by mass of the total of the components (A) to (D). With respect to 100 parts by mass of the total of the components (A) to (D), the effect of adhesion cannot be obtained when the component (C) is less than 0.5 parts by mass, and when it exceeds 30 parts by mass, the folding resistance of the film monomer ( (Bendability) disappears and the film cannot be formed.

(D)成分之有效量係依種類而異。(D)成分為酚系硬化劑、胺系硬化劑及酸酐系硬化劑時，相對於(A)至(D)成分之總和100質量份，(D)成分係以1至10質量份為佳。(D)成分為咪唑系硬化劑時，相對於(A)至(D)成分之總和100質量份，(D)成分係以0.1至5質量份為佳。 (D) The effective amount of the component varies depending on the kind. When the component (D) is a phenol-based hardener, an amine-based hardener, or an acid anhydride-based hardener, it is preferably 1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) to (D). . When the component (D) is an imidazole-based hardener, the component (D) is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total of the components (A) to (D).

從絕緣性、接著性及熱膨脹係數之觀點，相對於薄膜用樹脂組成物100質量份，(E)成分係以40至 95質量份為佳。(E)成分超出95質量份時，絕緣膜之接著力容易降低。另一方面，(E)成分未達40質量份時，即便絕緣填料之導熱率高，硬化後亦有導熱不足之虞。 From the viewpoints of insulation, adhesion, and thermal expansion coefficient, the (E) component ranges from 40 to 100 parts by mass based on 100 parts by mass of the resin composition for a film. 95 parts by mass is preferred. When the (E) component exceeds 95 parts by mass, the adhesion of the insulating film is liable to decrease. On the other hand, when the (E) component is less than 40 parts by mass, even if the thermal conductivity of the insulating filler is high, the thermal conductivity may be insufficient after curing.

而且，在不損及本發明之效果的範圍內，薄膜用樹脂組成物可包含增黏劑、消泡劑、流動調整劑、成膜助劑、分散助劑等添加劑，以及有機溶劑。 Moreover, as long as the effect of the present invention is not impaired, the resin composition for a film may include additives such as a tackifier, a defoamer, a flow regulator, a film-forming aid, and a dispersion aid, and an organic solvent.

有機溶劑方面，芳香族系溶劑係例如：甲苯、二甲苯等；酮系溶劑係例如：甲基乙基酮、甲基異丁基酮等。有機溶劑可單獨使用，亦可2種以上組合使用。而且，有機溶劑之使用量並無特別限定，以固形分成為20至50質量%之方式使用為佳。從作業性之觀點，薄膜用樹脂組成物之黏度以在200至3000mPa．s之範圍為佳。黏度係使用E型黏度計以轉速10rpm在25℃下測定而得之值。 In terms of organic solvents, aromatic solvents are, for example, toluene and xylene; ketone solvents are, for example, methyl ethyl ketone and methyl isobutyl ketone. The organic solvents may be used alone or in combination of two or more. In addition, the amount of the organic solvent used is not particularly limited, but it is preferably used so that the solid content becomes 20 to 50% by mass. From the viewpoint of workability, the viscosity of the resin composition for a film is 200 to 3000 mPa. The range of s is preferred. The viscosity is a value obtained by measuring at 25 ° C using an E-type viscometer at a rotation speed of 10 rpm.

薄膜用樹脂組成物可藉由將包含(A)至(E)成分等之原料於有機溶劑中溶解或分散等而獲得。將該等原料溶解或分散等之裝置並無特別限定，可使用具備攪拌及加熱裝置之研磨機、三輥研磨機、球磨機、行星式混合機及珠磨機等。並且，該等裝置可適當地組合使用。 The resin composition for a film can be obtained by dissolving or dispersing a raw material containing the components (A) to (E) and the like in an organic solvent. The apparatus for dissolving or dispersing such raw materials is not particularly limited, and a grinder, a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like provided with a stirring and heating device can be used. And, these devices can be used in appropriate combination.

[絕緣膜] [Insulation film]

本發明之絕緣膜係由上述薄膜用樹脂組成物所形成。 The insulating film of the present invention is formed of the resin composition for a thin film.

絕緣膜係藉由將薄膜用樹脂組成物塗佈在所要的支撐體之後進行乾燥而得。支撐體並無特別限定，可列舉如：銅、鋁等金屬箔，聚酯樹脂、聚乙烯樹脂、聚對苯二甲酸乙二酯樹脂等有機薄膜等。支撐體可使用矽氧 系化合物等施行脫模處理。 The insulating film is obtained by applying a resin composition for a thin film to a desired support and then drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, organic films such as polyester resin, polyethylene resin, and polyethylene terephthalate resin. Silicone The compound is subjected to a release treatment.

將薄膜用樹脂組成物塗佈在支撐體之方法並無特別限定，從薄膜化/調控薄膜厚度之觀點，係以微凹版塗佈法、狹縫式模具法、刮塗法為佳。由狹縫式模具法，在熱硬化後，可得到厚度10至300μm之絕緣膜。 The method for coating the resin composition for a film on a support is not particularly limited. From the viewpoint of thinning and controlling the thickness of the film, a micro gravure coating method, a slit die method, and a blade coating method are preferred. According to the slit die method, an insulating film having a thickness of 10 to 300 μm can be obtained after heat curing.

乾燥條件可依據薄膜用樹脂組成物所使用之有機溶劑之種類或量、塗佈厚度等而適當地設定，例如在50至120℃下可設為1至30分鐘左右。如此操作而得之絕緣膜具有良好的保存安定性。而且，絕緣膜可在所希望的時間點從支撐體剝離。 The drying conditions can be appropriately set according to the type or amount of the organic solvent used in the resin composition for a film, the coating thickness, and the like, and can be set to about 1 to 30 minutes at 50 to 120 ° C, for example. The insulating film obtained in this way has good storage stability. The insulating film can be peeled from the support at a desired time.

絕緣膜例如可在130至220℃、30至180分鐘使之熱硬化。 The insulating film can be thermally hardened, for example, at 130 to 220 ° C for 30 to 180 minutes.

絕緣膜之厚度係以10μm以上300μm以下為佳，以10μm以上100μm以下更佳，以10μm以上50μm以下又更佳。未達10μm時，有無法得到所要絕緣性之虞。超出300μm時，有半導體裝置之散熱性變差之虞。 The thickness of the insulating film is preferably from 10 μm to 300 μm, more preferably from 10 μm to 100 μm, and even more preferably from 10 μm to 50 μm. If it is less than 10 μm, the desired insulation property may not be obtained. If it exceeds 300 μm, the heat dissipation property of the semiconductor device may be deteriorated.

硬化後之絕緣膜的剝離強度係以超過5N/cm者為佳。 The peeling strength of the cured insulating film is preferably more than 5 N / cm.

硬化後之絕緣膜的體積電阻率，亦即，硬化後之薄膜用樹脂組成物的體積電阻率以1×1010Ω．cm以上為佳，體積電阻率以1×1012Ω．cm以上更佳，以1×1013Ω．cm以上又更佳。並且，硬化後之絕緣膜的導熱率，亦即，硬化後之薄膜用樹脂組成物的導熱率以1.0W/m‧K以上更佳。硬化後之絕緣膜的體積電阻率未達1×1010Ω．cm時， 有無法滿足半導體裝置所需的絕緣性之虞。並且，硬化後之絕緣膜的導熱率未達1.0W/m‧K時，有半導體裝置之散熱性變差之虞。硬化後之絕緣膜的體積電阻率與導熱率可由(E)成分之種類與含量而調控。 The volume resistivity of the cured insulating film, that is, the volume resistivity of the resin composition for the thin film after curing is 1 × 10 10 Ω. Above cm is preferred, and the volume resistivity is 1 × 10 12 Ω. Above cm is better, with 1 × 10 13 Ω. Above cm is even better. In addition, the thermal conductivity of the cured insulating film, that is, the thermal conductivity of the resin composition for a thin film after curing is preferably 1.0 W / m‧K or more. The volume resistivity of the hardened insulating film is less than 1 × 10 10 Ω. At cm, there is a possibility that the insulation required for a semiconductor device cannot be satisfied. In addition, when the thermal conductivity of the cured insulating film is less than 1.0 W / m · K, the heat dissipation property of the semiconductor device may be deteriorated. The volume resistivity and thermal conductivity of the cured insulating film can be controlled by the type and content of the (E) component.

[半導體裝置] [Semiconductor device]

本發明之半導體裝置係包含上述絕緣膜之硬化物。半導體裝置方面，係可列舉如：模組或電子零件等發熱體與基板以絕緣膜之硬化物使接著者、或基板與散熱板以絕緣膜之硬化物使接著者。 The semiconductor device of the present invention is a cured product including the above-mentioned insulating film. In terms of semiconductor devices, for example, a heating element such as a module or an electronic component and a substrate are hardened by an insulating film, and the substrate or a heat sink is fixed by a hardened material of the insulating film.

[實施例] [Example]

以實施例說明本發明，惟本發明並不僅限於該等。而且，以下之實施例中，除非另行說明，否則份、%係表示質量份、質量%。 The present invention is illustrated by examples, but the present invention is not limited to these. In the following examples, parts and% are parts by mass and mass% unless otherwise specified.

[實施例1至6、比較例1至3] [Examples 1 to 6, Comparative Examples 1 to 3]

以表1所示的調配，將(A)成分、(B)成分、(C)成分及適量的甲苯稱量調配後，將該等投入加溫至80℃的反應釜中，於150rpm旋轉速之旋轉下，進行常壓混合3小時，製作透明劑。在所製作之透明劑中，加入(D)成分、(E)成分及其它成分並以行星式混合機分散，製作成薄膜用樹脂組成物。將如此操作所得之薄膜用樹脂組成物塗佈在作為支撐體之經施加脫模處理之PET薄膜的單面上，在100℃下乾燥，得到附有支撐體的絕緣膜。比較例2係無法成形為薄膜，亦無法施行下述之導熱率、剝離強度的評定。並且，實施例1至6之硬化後的薄膜用樹脂組成物之體積電 阻率均為1×1010Ω．cm以上。具體上，實施例1為1.5×1014Ω．cm、實施例2為2.1×1014Ω．cm。硬化後的薄膜用樹脂組成物之體積電阻率係以經壓機熱硬化(200℃、60分鐘、0.1MPa)後之薄膜用樹脂組成物作為試驗片，並以東亞電波工業公司製作之極超絕緣計(型號：SM-8220)測定試驗片之體積電阻率。 (A) component, (B) component, (C) component and appropriate amount of toluene were prepared according to the preparation shown in Table 1, and then put into a reaction kettle heated to 80 ° C, and rotated at 150 rpm. Under the rotation, the mixture was mixed under normal pressure for 3 hours to prepare a transparent agent. (D) component, (E) component, and other components were added to the produced transparent agent, and were disperse | distributed by the planetary mixer, and the resin composition for films was produced. The resin composition for a film obtained in this way was coated on one side of a PET film that was subjected to a release treatment as a support, and dried at 100 ° C to obtain an insulating film with a support. Comparative Example 2 cannot be formed into a thin film, and the following evaluations of thermal conductivity and peel strength cannot be performed. In addition, the volume resistivities of the resin compositions for thin films after curing in Examples 1 to 6 were all 1 × 10 10 Ω. cm or more. Specifically, Example 1 is 1.5 × 10 14 Ω. cm, Example 2 is 2.1 × 10 14 Ω. cm. The volume resistivity of the hardened resin composition for thin films is based on the resin composition for thin films after thermal curing at a press (200 ° C, 60 minutes, 0.1 MPa) as a test piece. Insulation meter (model: SM-8220) measures the volume resistivity of the test piece.

[導熱率之評定] [Evaluation of thermal conductivity]

將未硬化之絕緣膜以壓機使熱硬化(200℃、60分鐘、0.1MPa)。硬化之絕緣膜的導熱率係以NETZSCH公司製造的熱導儀(氙閃光分析儀，型號：LFA447 Nanoflash)測定。 The non-hardened insulating film was thermally hardened by a press (200 ° C, 60 minutes, 0.1 MPa). The thermal conductivity of the hardened insulating film was measured with a thermal conductivity meter (xenon flash analyzer, model: LFA447 Nanoflash) manufactured by NETZSCH.

[剝離強度之評定] [Evaluation of peel strength]

在絕緣膜兩面，以粗糙面作為內側並貼合銅箔，再以壓機進行熱壓接(200℃、60分鐘、0.1MPa)。將該試驗片裁成10mm寬，並以自動立體測圖儀剝離，測定剝離強度。對於測定結果係計算各N=5之平均值。 On both sides of the insulating film, a copper foil was bonded with the rough surface as an inner side, and then thermal compression bonding was performed with a press (200 ° C, 60 minutes, 0.1 MPa). This test piece was cut to a width of 10 mm and peeled with an autostereograph to measure the peel strength. For the measurement results, an average value of each N = 5 was calculated.

由表1可知，實施例1至7全部係使用絕緣性、耐熱成分優異之(A)成分，且即使含有75質量份以上之(E)成分，膜成形性亦佳，硬化後之導熱率、剝離強度均高。相對於此，由表1可知，(C)成分過少之比較例1係剝離強度不足。並且，(C)成分過多之比較例2的膜成形性不佳。使用聯苯型環氧樹脂取代(C)成分之比較例3係剝離強度明顯降低。 As can be seen from Table 1, all of Examples 1 to 7 used the (A) component having excellent insulation and heat-resistant components, and even containing (E) component in an amount of 75 parts by mass or more, the film had good film formability, thermal conductivity after curing, All peel strengths are high. In contrast, from Table 1, it can be seen that Comparative Example 1 which has too little (C) component has insufficient peel strength. In addition, Comparative Example 2 having too much (C) component had poor film formability. In Comparative Example 3, where a biphenyl epoxy resin was used instead of the component (C), the peel strength was significantly reduced.

如上所述，本發明之薄膜用樹脂組成物之膜成形性良好，硬化後，導熱率與剝離強度高，在製造可靠性高的半導體裝置上極為有用。 As described above, the film-forming resin composition of the present invention has good film formability, has high thermal conductivity and peel strength after curing, and is extremely useful for manufacturing a semiconductor device with high reliability.

Claims (6)

一種薄膜用樹脂組成物，其特徵係：包含下述(A)、(B)、(C)、(D)與(E)，且相對於(A)成分、(B)成分、(C)成分及(D)成分之總和100質量份，(A)成分為10至60質量份，(B)成分為10至60質量份，(C)成分為0.5至30.0質量份，(D)成分為0.1至10質量份，相對於薄膜用樹脂組成物100質量份，(E)成分為40至95質量份，(A)以下通式(1)所示之兩末端至少具有鍵結有乙烯基的苯基之聚醚化合物、(B)熱塑性彈性體、(C)萘型環氧樹脂、(D)硬化劑、(E)絕緣填料，
Figure TWI628229B_C0001
Figure TWI628229B_C0002
Figure TWI628229B_C0003
(式中，R1、R2、R3、R4、R5、R6及R7可相同或相異，係氫原子、鹵原子、烷基、鹵烷基或苯基；-(O-X-O)-係以構造式(2)表示，其中，R8、R9、R10、R14及R15可相同或相異，係鹵原子或碳數6以下之烷基或苯基，R11、R12及R13可相同或相異，係氫原子、鹵原子、或碳數6以下之烷基或苯基；-(Y-O)-係構造式(3)所示之1種構造、或構造式(3)所示之2種以上之構造經隨機排列者，其中，R16及R17可相同或相異，係鹵原子或碳數6以下之烷基或苯基，R18及R19可相同或相異，係氫原子、鹵原子或碳數6以下之烷基或苯基；Z為碳數1以上之有機基，視情況可包含氧原子、氮原子、硫原子及鹵原子；a、b之至少一者不為0，表示0至300之整數；c、d表示0或1之整數)。A resin composition for a film, characterized by comprising the following (A), (B), (C), (D) and (E), relative to (A) component, (B) component and (C) The total of the component and (D) component is 100 parts by mass, (A) component is 10 to 60 parts by mass, (B) component is 10 to 60 parts by mass, (C) component is 0.5 to 30.0 parts by mass, (D) component is 0.1 to 10 parts by mass, (E) component is 40 to 95 parts by mass relative to 100 parts by mass of the resin composition for film, (A) both ends of the following general formula (1) have at least a vinyl group bonded Phenyl polyether compound, (B) thermoplastic elastomer, (C) naphthalene epoxy resin, (D) hardener, (E) insulating filler,
Figure TWI628229B_C0001
Figure TWI628229B_C0002
Figure TWI628229B_C0003
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different, and are hydrogen atom, halogen atom, alkyl group, haloalkyl group or phenyl group; -(OXO )- is represented by structural formula (2), wherein R 8 , R 9 , R 10 , R 14 and R 15 may be the same or different, and are a halogen atom or an alkyl group or phenyl group having 6 or less carbon atoms, R 11 , R 12 and R 13 may be the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group or a phenyl group having 6 or less carbon atoms; -(YO)- is a structure shown in structural formula (3), or If two or more structures shown in structural formula (3) are randomly arranged, R 16 and R 17 may be the same or different, and are a halogen atom or an alkyl group or phenyl group having 6 or less carbon atoms, R 18 and R 19 may be the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group or a phenyl group with a carbon number of 6 or less; Z is an organic group with a carbon number of 1 or more, and may include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom as appropriate ; At least one of a and b is not 0, which means an integer from 0 to 300; c, d means an integer of 0 or 1.) 如申請專利範圍第1項所述之薄膜用樹脂組成物，其中，(E)成分係選自MgO、Al2O3、AlN、BN、鑽石填料、ZnO及SiC所成組群中之至少1種。The resin composition for thin films as described in item 1 of the patent application, wherein the (E) component is at least 1 selected from the group consisting of MgO, Al 2 O 3 , AlN, BN, diamond filler, ZnO and SiC Species. 如申請專利範圍第1或2項所述之薄膜用樹脂組成物，其中，硬化後之薄膜用樹脂組成物之體積電阻率為1×1010Ω‧cm以上。The resin composition for thin films as described in item 1 or 2 of the patent application range, wherein the volume resistivity of the resin composition for thin films after curing is 1×10 10 Ω‧cm or more. 如申請專利範圍第1或2項所述之薄膜用樹脂組成物，其中，相對於(A)成分、(B)成分、(C)成分及(D)成分之總和100質量份，當(D)成分為酚系硬化劑、胺系硬化劑、酸酐系硬化劑時，(D)成分為1至10質量份，當(D)成分為咪唑系硬化劑時，(D)成分為0.1至5質量份。The resin composition for films as described in item 1 or 2 of the patent application scope, wherein, relative to the total of 100 parts by mass of (A) component, (B) component, (C) component and (D) component, when (D ) When the component is a phenol-based hardener, an amine-based hardener, or an acid anhydride-based hardener, the (D) component is 1 to 10 parts by mass, and when the (D) component is an imidazole-based hardener, the (D) component is 0.1 to 5 Quality parts. 一種絕緣膜，係由如申請專利範圍第1至4項中任一項所述之薄膜用樹脂組成物所形成者。An insulating film is formed of the resin composition for thin films as described in any one of items 1 to 4 of the patent application. 一種半導體裝置，係包含如申請專利範圍第5項所述之絕緣膜的硬化物者。A semiconductor device comprising a cured product of an insulating film as described in item 5 of the patent application.
TW103133904A 2013-10-08 2014-09-30 Film forming resin composition, insulating film and semiconductor device TWI628229B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013211444A JP6230363B2 (en) 2013-10-08 2013-10-08 Resin composition for film, insulating film, and semiconductor device
JP2013-211444 2013-10-08

Publications (2)

Publication Number Publication Date
TW201516088A TW201516088A (en) 2015-05-01
TWI628229B true TWI628229B (en) 2018-07-01

Family

ID=52812894

Family Applications (1)

Application Number Title Priority Date Filing Date
TW103133904A TWI628229B (en) 2013-10-08 2014-09-30 Film forming resin composition, insulating film and semiconductor device

Country Status (5)

Country Link
JP (1) JP6230363B2 (en)
KR (1) KR102187491B1 (en)
CN (1) CN105593300A (en)
TW (1) TWI628229B (en)
WO (1) WO2015053074A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102460328B1 (en) * 2015-08-17 2022-10-28 세키스이가가쿠 고교가부시키가이샤 Semiconductor device, and semiconductor element protection material
JP6857895B2 (en) * 2016-03-17 2021-04-14 ナミックス株式会社 Resin composition, thermosetting film, cured product, printed wiring board, semiconductor device
CN108299796B (en) * 2017-12-30 2020-12-15 苏州赛尔科技有限公司 Resin-based diamond scribing knife for LED segmentation and preparation method thereof
JP7020332B2 (en) * 2018-07-26 2022-02-16 味の素株式会社 Resin composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200617086A (en) * 2004-08-19 2006-06-01 Mitsubishi Gas Chemical Co Curable resin composition, curable film and cured film
TW200813124A (en) * 2006-08-08 2008-03-16 Namics Corp Thermosetting resin composition and a un-cured film constituted by such thermosetting resin composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5115135B2 (en) * 2007-10-15 2013-01-09 三菱瓦斯化学株式会社 Curable resin composition and cured product
JP5233710B2 (en) * 2008-02-12 2013-07-10 三菱瓦斯化学株式会社 Resin composition, prepreg and metal foil-clad laminate
JP5348740B2 (en) 2008-06-23 2013-11-20 日本化薬株式会社 Epoxy resin, epoxy resin composition, and cured product thereof
JP5463110B2 (en) * 2009-09-24 2014-04-09 ナミックス株式会社 Coverlay film
JP5737129B2 (en) 2010-10-18 2015-06-17 三菱化学株式会社 Epoxy resin, epoxy resin composition and cured product
KR20130074955A (en) * 2011-12-27 2013-07-05 도레이첨단소재 주식회사 Copper clad laminate and coverlay film using a non-halogen type adhesive
JP5955156B2 (en) * 2012-08-10 2016-07-20 ナミックス株式会社 Resin composition, and adhesive film and coverlay film thereby
WO2014148155A1 (en) * 2013-03-22 2014-09-25 ナミックス株式会社 Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200617086A (en) * 2004-08-19 2006-06-01 Mitsubishi Gas Chemical Co Curable resin composition, curable film and cured film
TW200813124A (en) * 2006-08-08 2008-03-16 Namics Corp Thermosetting resin composition and a un-cured film constituted by such thermosetting resin composition

Also Published As

Publication number Publication date
JP6230363B2 (en) 2017-11-15
TW201516088A (en) 2015-05-01
CN105593300A (en) 2016-05-18
JP2015074712A (en) 2015-04-20
WO2015053074A1 (en) 2015-04-16
KR102187491B1 (en) 2020-12-07
KR20160067890A (en) 2016-06-14

Similar Documents

Publication Publication Date Title
KR101523144B1 (en) Epoxy composites with improved heat dissipation, and their applications for thermal conductive and dissipative products
TWI520926B (en) A ceramic mixture, and a thermoconductive resin sheet containing a ceramic composition
TWI468483B (en) Thermal follower
TWI628229B (en) Film forming resin composition, insulating film and semiconductor device
JP6945241B2 (en) Resin composition for film, film, film with base material, metal / resin laminate, cured resin, semiconductor device, and film manufacturing method
JP6570259B2 (en) Resin composition, insulating film, and semiconductor device
TWI599634B (en) Semiconductor device
KR20150140125A (en) Aluminum powder and graphite composite including a thermally conductive resin composition and dissipative products
KR101703558B1 (en) Alumina and graphite composite including a thermally conductive resin composition and dissipative products
TWI694126B (en) Resin composition, adhesive film and semiconductor device
JP7188070B2 (en) LAMINATED STRUCTURE WITH RADIATION INSULATING SHEET AND CURED SHEET AS INSULATING LAYER
JP6747440B2 (en) Resin composition for film formation, sealing film using the same, sealing film with support, and semiconductor device
KR101749459B1 (en) Aluminum powder and graphite composite including a thermally conductive resin composition and dissipative products
TWI663195B (en) Insulating film and semiconductor device
KR102483123B1 (en) Thermally conductive resin composition
KR101447258B1 (en) Thermal conductive epoxy composites and their applications for light emitting diode fixtures
JP6715033B2 (en) Heat conductive adhesive composition, heat conductive adhesive sheet and method for producing laminated body
JPWO2020075663A1 (en) Resin composition, resin cured product and composite molded product
JP6912030B2 (en) Resin compositions, adhesive films, and semiconductor devices
CN104603935B (en) Semiconductor device