CN1555405A - Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition - Google Patents

Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition Download PDF

Info

Publication number
CN1555405A
CN1555405A CNA028179056A CN02817905A CN1555405A CN 1555405 A CN1555405 A CN 1555405A CN A028179056 A CNA028179056 A CN A028179056A CN 02817905 A CN02817905 A CN 02817905A CN 1555405 A CN1555405 A CN 1555405A
Authority
CN
China
Prior art keywords
cationically polymerizable
composition
binder composition
epoxy
adhesive composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA028179056A
Other languages
Chinese (zh)
Other versions
CN1289621C (en
Inventor
山口裕显
司
弘重裕司
太
秋山良太
北村哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of CN1555405A publication Critical patent/CN1555405A/en
Application granted granted Critical
Publication of CN1289621C publication Critical patent/CN1289621C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • H01L24/83—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • H01L2224/2929—Material of the matrix 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29301—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H01L2224/29311—Tin [Sn] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29317—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950°C
    • H01L2224/29318—Zinc [Zn] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29344—Gold [Au] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29347—Copper [Cu] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29355—Nickel [Ni] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/2936—Iron [Fe] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29363—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than 1550°C
    • H01L2224/29364—Palladium [Pd] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29363—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than 1550°C
    • H01L2224/29369—Platinum [Pt] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29363—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than 1550°C
    • H01L2224/2938—Molybdenum [Mo] as principal constituent
    • 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
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29363—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than 1550°C
    • H01L2224/29384—Tungsten [W] as principal constituent
    • 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
    • H01L2224/80—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
    • H01L2224/83851—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester being an anisotropic conductive adhesive
    • 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
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01012—Magnesium [Mg]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • 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
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
    • H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
    • 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
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesive Tapes (AREA)

Abstract

A cationic polymerizable adhesive composition comprising a cationic polymerizable monomer selected from an epoxy monomer, a vinyl ether monomer and a mixture thereof, a cationic polymerization catalyst and a stabilizer, wherein the stabilizer is at least one acid amide represented by the following Formula (I) wherein R1 is an alkyl group having from 1 to 30 carbon atoms or an alkenyl group containing one or two unsaturated bond(s) and having from 2 to 30 carbon atoms, and each R2 is independently hydrogen or an alkyl group having from 1 to 10 carbon atoms.

Description

The binder composition of cationically polymerizable and anisotropic-electroconductive adhesive composition
Detailed description of the invention
The present invention relates to show the cationically polymerizable binder composition of splendid bond strength, and can show satisfactory electrical conductivity or thermal conductivity, and show the anisotropic conductive or the heat-conductive bonding agent composition of splendid bond strength simultaneously.
Utilize the cationically polymerizable composition of cationoid polymerisation to have purposes widely, for example, in coating and printing ink and adhesive field.Especially, in the use of tackiness agent, because its high solidification rate and avoid oxygen retardance, the cationically polymerizable composition is favourable.Yet bond strength can take place and reduce in the rapidly-curable of cationically polymerizable composition in some cases.Especially, if binder composition is to apply fully and spread on the adherend, and, just can not obtain sufficiently high bond strength before contacting with adherend is surperficial because carrying out fast of reaction then solidified.In order to address this problem, select cationically polymerizable compound and polymerizing catalyst, they have low reactivity respectively, its degree does not influence at the curing performance that requires under the temperature, perhaps, adding can suppress binder composition polymeric stablizer, all is effective.By these methods, the storage stability of cationically polymerizable composition also is improved simultaneously.
For example, Japanese unexamined patent publication (disclosing) 4-227625, described special amine has been joined in the composition epoxy resin as stablizer, said composition comprises Resins, epoxy and special iron-aromatic hydrocarbons complex initiator, and stated adding by this amine, even composition epoxy resin is by after the optical radiation activation, guarantee more than 30 days at the storage stability of room temperature, and composition can be at high temperature rapid curing.
Japanese unexamined patent publication (disclosing) but 8-511572 has described the energy polymeric composition that comprises cationic curable monomer, organometallic ligand cationic salts and special stabilization additives, and set forth:, improve said composition storage stability and working life by having this formation.
Japanese unexamined patent publication (disclosing) 5-262815, the reactive composition that contains cationically polymerizable compound and hot latent catalyst has been described, this hot latent catalyst comprises that Lewis acid reaches the title complex to electron compound, and set forth: by having this formation, improve the storage stability of composition, and given polymkeric substance splendid physicals.
On the other hand, in liquid-crystal display, the electrod assembly of glass display panel activates the required drive IC of display panel, is called being connected of TCP (carrier band encapsulation) flexible circuit with top installation, is by inserting anisotropic conductive adhesive film heat pressure adhesive.Connect spacing and be generally the 100-200 micron.Yet, because that display unit becomes is very limited, connect spacing become thinner, recent years, require to connect 50 microns of spacings or below.This thinner connection spacing is because the heat during heat pressure adhesive, by expansion and the contraction of TCP, and the problem that causes spacing to slide.In order to address this problem, need be at the anisotropic conductive adhesion film of lower temperature energy heat pressure adhesive.And, in order to improve throughput, also need the anisotropic conductive adhesive film of energy heat pressure adhesive within a short period of time.In order to satisfy these requirements, the anisotropic conductive adhesive film that uses cationic polymerization mechanism and have hyperergy has been proposed.
For example, Japanese unexamined patent publication (disclosing) 8-511570, the anisotropic-electroconductive adhesive composition has been described, it comprises curable Resins, epoxy, thermoplastic resin, organo-metallic complex cation, stabilization additives, solidification rate toughener and conductive particle, and be set forth in temperature 120-125 ℃, can reach thermofixation.
The problem that invention solves
By the use of these stablizers, improve the storage life of the binder composition that obtains, and heat pressure adhesive can be carried out at low temperature, still, bond strength is not high enough.
The purpose of this invention is to provide the cationically polymerizable binder composition with the storage life-span of living forever, it can be bonding at low temperature and pressure, and guarantee splendid bond strength.
The method of dealing with problems
In order to address the above problem, the invention provides the cationically polymerizable binder composition, it comprises that (A) is selected from the cationically polymerizable monomer of epoxy monomer, vinyl ether monomers and composition thereof, (B) cationic polymerisation catalyst and (C) stablizer, wherein at least a acid amides by following molecular formula (I) expression is used as (C) stablizer:
Figure A0281790500041
(R wherein 1Be alkyl, perhaps, contain one or two unsaturated link(age) and the alkenyl with 2-30 carbon atom, R with 1-30 carbon atom 2Be respectively hydrogen or alkyl) with 1-10 carbon atom.
According to the present invention, above-mentioned cationically polymerizable binder composition is provided, and comprises conduction or the anisotropic conductive of heat conduction particle or the binder composition of heat conduction.
The mode that carries out an invention
As mentioned above, cationically polymerizable binder composition of the present invention is by (A) cationically polymerizable monomer, and (B) cationic polymerisation catalyst is formed as stablizer with the acid amides of (C) molecular formula (1) expression.Each constitutes component, is described below.
The cationically polymerizable monomer
The cationically polymerizable monomer is selected from epoxy monomer, vinyl ether monomers and composition thereof.The example of epoxy monomer comprises having 1 of cationically polymerizable functional group respectively, the 2-cyclic ethers, and 1,3-cyclic ethers and 1, the 4-cyclic ethers, but epoxy monomer is limited to and does not suppress the cationoid polymerisation group, for example contains the monomer of the functional group of amine, sulphur or phosphorus.The preferred cycloaliphatic epoxy resin of this epoxy monomer or contain the Resins, epoxy of glycidyl.
Cycloaliphatic epoxy resin is the compound that has average 2 or more a plurality of alicyclic epoxy groups in the molecule, its example comprises the compound that has two epoxide groups in the molecule, as the vinyl cyclohexene dioxide (for example, ERL-4206, Union Carbide Japan produces), 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate (for example, UVR-6105 and UVR-6110, Union Carbide Japan produces), hexanodioic acid two (3,4-epoxy hexamethylene) ester (for example UVR-6128, Union Carbide Japan produce) and 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy) hexanaphthene--dioxane (for example, ERL-4234, Union Carbide Japan produces), have 3 with intramolecularly, 4 or the multifunctional cycloaliphatic epoxy resin of more a plurality of epoxide groups (for example, Epolide GT, Daicel ChemicalIndustries Ltd. produces).
The epoxy equivalent (weight) of cycloaliphatic epoxy resin is generally 90-500, preferred 100-400, more preferably 120-300, most preferably 210-235.If epoxy equivalent (weight) is less than 90, toughness after the thermofixation and bond strength can reduce, cause connection reliability to reduce, if but epoxy equivalent (weight) surpasses 500, the viscosity of whole system increases excessively, and its result presents bad flowability at heat pressure adhesive, perhaps reduce reactivity, thereby reduce the reliability that connects.
The Resins, epoxy that contains the Racemic glycidol group is the compound that has average two or more Racemic glycidol groups in the molecule, its example (for example comprises the bisphenol A-type glycidyl ether, Epikote 828, Yuka Shell Epoxy produces) and the phenolic varnish type epoxy is (for example, Epikote 154, and Yuka Shell Epoxy K.K. produces).
The epoxy equivalent (weight) that contains the Resins, epoxy of Racemic glycidol group is generally 170-5500, preferred 170-1000, more preferably 170-500, most preferably 175-210.If epoxy equivalent (weight) is less than 170, toughness after the thermofixation and bond strength can reduce, if but epoxy equivalent (weight) surpasses 5500, the viscosity of whole system increases excessively, and its result presents bad flowability at heat pressure adhesive, perhaps reduce reactivity, thereby reduce the reliability that connects.
Vinyl ether monomers has the high electron density of two keys, forms highly stable carbon oxonium ion, so this monomer has high reactivity in cationoid polymerisation.In order not suppress cationoid polymerisation, vinyl ether monomers is limited to unazotized, and its example comprises methylvinylether, ethyl vinyl ether, tert-Butyl vinyl ether, IVE, triethylene glycol divinyl ether and 1,4 cyclohexane dimethanol divinyl ether.The example of preferred vinyl ether monomers comprises triethylene glycol divinyl ether (for example, Rapi-Cure DVE-3, ISP Japan K.K. production) and cyclohexanedimethanol divinyl ether (for example, Rapi-Cure CHVE, ISP Japan K.K. production).
These epoxy monomers and vinyl ether monomers can use respectively and use as its mixture.Can use a large amount of epoxy monomers and vinyl ether monomers.Especially, preferably use cycloaliphatic epoxy resin and the mixture that contains Racemic glycidol group Resins, epoxy.Cycloaliphatic epoxy resin has the rapidly-curable of improvement binder composition and the effect of curability at low temperatures, and because its low viscosity also has the effect of raising binder composition to the adherend adhesion.On the other hand, the Resins, epoxy that contains the Racemic glycidol group has the effect that prolongs the binder composition serviceable time after activation.Therefore, by being used in combination cycloaliphatic epoxy resin and containing Racemic glycidol group Resins, epoxy, the binder composition that obtains can show the low temperature rapidly-curable of good cycloaliphatic epoxy resin and contain the over-all properties of the room temperature prolonged storage stability of Racemic glycidol group Resins, epoxy.The ratio of cycloaliphatic epoxy resin/contain Racemic glycidol group Resins, epoxy fusion is generally 5: 95-98: 2, preferred 40: 60-94: 6, more preferably 50: 50-80: 20.If the amount of cycloaliphatic epoxy resin is lower than 5 weight % (in cycloaliphatic epoxy resin and the total amount that contains Racemic glycidol group Resins, epoxy), cryogenic curing performance can reduce, thereby can not provide sufficiently high bond strength and connection reliability, if but the amount of cycloaliphatic epoxy resin surpasses 98 weight %, even near room temperature, curing reaction also carries out easily, and therefore, the serviceable time after the activation can shorten.The monomeric blended amount of cationically polymerizable is the whole composition of from 10 to 90 weight parts/100 weight parts preferably.
Cationic polymerisation catalyst
Cationic polymerisation catalyst is under ultraviolet radiation or produces the compound such as the Lewis acid of cation activity center and catalysis oxirane ring ring-opening reaction under heating and catalysis.The example of this cationic polymerisation catalyst comprises aryl diazonium salts, diaryl group iodized salt, triarylsulfonium salt, triaryl selenium salt and iron-aromatic hydrocarbons title complex.In the middle of them; iron-aromatic hydrocarbons title complex is because their thermostability is particularly preferred; its object lesson comprises that dimethylbenzene-cyclopentadiene closes iron (II) (three (trifluoromethyl sulfonyl) methide; phosphofluoric acid isopropyl benzene-cyclopentadiene closes iron (II) and two (η-1; 3, the 5-Three methyl Benzene) iron (II) three (trifluoromethyl sulfonyl) methide.Other example of cationic polymerisation catalyst discloses in Japanese unexamined patent publication 8-511572.
The cationic polymerisation catalyst consumption is generally the cationically polymerizable monomer of per 100 weight parts, from 0.05 to 10.0 weight part, and preferred from 0.075 to 7.0 weight part, more preferably from the 0.1-4.0 weight part, from 1.0 to 2.5 weight parts most preferably.If consumption is less than 0.05 weight part, can be reduced at cryogenic curing performance to provide sufficiently high bond strength and connection reliability, if but it surpasses 10.0 weight parts, even near room temperature, curing reaction also carries out easily, so, can reduce at the storage stability of room temperature.
Stablizer
Stablizer has the effect of effective control binder composition solidification rate of the present invention.In the present invention, stablizer is the acid amides with this spline structure: the hydrogen of ammonia or amine is by acyl substituted, shown in top molecular formula (I).
The object lesson of acid amides comprises ethanamide, propionic acid amide, positive butyramide, laurylamide, N,N-dimethylacetamide, oil (acid) acid amides and erucicamide.
The whole binder composition of the preferred 0.000005-0.02 weight part of the blended amount of stablizer/100 weight parts.Stablizer is to the preferred 0.03-1.0 of the equivalent of cationic polymerisation catalyst.If blended amount is less than 0.03, estimate the unable to get up stabilizer function, if but it surpasses 1.0, and be bad to the bond properties of adherend.The preferred 0.05-0.8 of equivalent, preferred 0.1-0.5.
By mixing these cationically polymerizable monomers, cationic polymerisation catalyst and stablizer can obtain cationically polymerizable binder composition of the present invention.By conductive particle being joined this binder composition, can obtain the anisotropic-electroconductive adhesive composition, by adding heat conduction particle, can obtain the heat-conductive bonding agent composition.
The example of spendable conductive particle comprises conductive particle, as carbon granule and copper, nickel, gold, tin, zinc, platinum, palladium, iron, tungsten, molybdenum, metallic particles such as scolding tin.Also can after further covering particle surface, use these particles with the conductive coating of metal etc.And, also can use the non-conductive of granulated glass sphere, silica, graphite, pottery or polymkeric substance such as polyethylene, polystyrene, phenol resins, Resins, epoxy, acrylic resin and benzo guanamine resin, their surface covers with the conductive coating of metal etc.The shape of conductive particle has no particular limits, but preferred usually near spherical.This particle can have coarse a little or the surface of spike is arranged.Shape is ellipticity or oval column also.
The mean particle size of the conductive particle that uses can change according to the interval between electrode width that is used to connect and the adjacent electrode.For example, 50 microns of electrode widths, under the situation of the interval between adjacent electrode 50 microns (being 100 microns of interelectrode distances), mean particle size is suitably for the micron at 3-20.By using the anisotropic conductive adhesive film, the conductive particle of mean particle size in this scope is dispersed in this film, can obtain enough good conductive characteristic, simultaneously, can prevent the short circuit between the adjacent electrode well.Because being used for the interconnective interelectrode distance of circuit substrate is generally the 50-1000 micron, the preferred 2-40 micron of the mean particle size of conductive particle.If mean particle size is less than 2 microns, particle is embedded in the pit on the electrode surface, can not play the function of conductive particle, if but it surpasses 40 microns, is easy between the adjacent electrode be short-circuited.
The add-on of conductive particle can change according to the area of electrode used therein and the mean particle size of conductive particle.When having some conductive particles (for example from 2-10) individual on each electrode, can obtain good connection usually.Under the situation that reduces resistance again, conductive particle can be blended in the tackiness agent, like this, has 10-300 conductive particle.And, when heat pressure adhesive, using under the highly compressed situation, the number of conductive particle rises to 300-1000 on the electrode, with dispersive pressure, thereby reaches good connection.Not comprise the tackiness agent cumulative volume of conductive particle, the amount of conductive particle is generally 0.1-30 volume %, preferred 0.5-10 volume %, more preferably 1-5 volume %.If this amount does not have conductive particle probably less than 0.1 volume % on electrode when bonding, connection stability can reduce, if but this amount surpasses 30 volume %, is easy between the adjacent electrode be short-circuited.
By heat conduction particle being joined the heat-conductive bonding agent composition that obtains in the cationically polymerizable binder composition of the present invention, be used for thermal source, for example, between electronic unit and the radiator element, or between electronic unit and the circuit substrate, as the heat transfer interface in the thermal source heat distribution.The example of spendable heat conduction particle comprises the particle of aluminum oxide, silica, boron nitride, magnesium oxide and carbon fiber.The shape of heat conduction particle is not limited to particle form, but can use different shape, as plate and spicule.Consider their purposes, the heat conduction particle size is preferably the 0.1-500 micron.Also can be used in combination and have varigrained heat conduction particle.Heat conduction particle is to the ratio of 100 weight part binder compositions, preferred 100-1000 part.
Anisotropic conductive or heat-conductive bonding agent composition preferably use with the form of film.Film can obtain by the coating solution that preparation in suitable organic solvent contains binder composition, organic solvent such as methyl ethyl ketone (MEK), with coating solution with on coating method (as the blade coating device) the paint shim that is fit to, and dry coating film.At this moment, can on surface of shim or two surfaces, form the peel ply of silica-based or fluorine-based stripper.Using under the situation of ultraviolet activated form polymerizing catalyst as cationic polymerisation catalyst, forming the film with organic solvent, can obtain film by the hot melt and the extrusion moulding of binder composition except recited above.Unless ultraviolet radiation and even 100 ℃ of temperature or abovely also reacted hardly to several hours time with several minutes, ultraviolet activated form cationic polymerisation catalyst is very heat-staple.The preferred 5-100 micron of the film thickness of Xing Chenging like this, reaching essential good filling, thereby when circuit substrate is interconnected by heat pressure adhesive in interconnecting piece, do not have the gap.
According to end-use, except that said components, cationically polymerizable binder composition of the present invention also can contain other additive.The examples of additives that can be added in the binder composition (for example comprises cationoid polymerisation promotor, the oxalic acid di tert butyl carbonate), antioxidant (for example, the phenol-based anti-oxidants of being obstructed), glycol (for example two (phenoxyethyl alcohol) fluorenes), coupler (for example, silane coupling agent is as γ-glycidoxypropyltrime,hoxysilane and β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane), chain transfer agents, sensitizing agent (for example, anthracene), tackifier, thermoplastic elastomer or resin, filler (for example, silica), flowing regulator, softening agent, defoamer and colorant.And, also can add the stablizer that does not comprise acid amides.Their example comprises by being captured in Lewis acid that is used as cationic species in the cationoid polymerisation etc., suppress or forbid the stablizer of cationic polymerization, their object lesson comprises crown ether, as 15-hat-5,1,10-phenanthroline and derivative thereof, Tolylamine is as N, N-diethyl-meta-aminotoluene, phosphine, as triphenylphosphine, and triazine.
Thermoplastic elastomer or resin preferably add when cationically polymerizable binder composition of the present invention forms adhesive film.Thermoplastic elastomer or resin increase the film-forming properties of adhesive film, simultaneously, improve the shock-resistance of adhesive film, reduce the residual internal stress that curing reaction produces, and improve adhesion reliability.Thermoplastic elastomer is a kind of polymerizable compound that is commonly referred to thermoplastic elastomer below a certain temperature, and they are by forming with soft section that shows caoutchouc elasticity as limited hard mutually section.This elastomeric example comprises styrenic based thermoplastic elastomer.Styrene-based elastomer is a segmented copolymer, for example: comprise styrene units in hard section, comprise polyhutadiene or polyisoprene units in soft section.Their exemplary comprises styrene-butadiene-styrene block copolymer (SBS) and styrene isoprene styrene block copolymer (SIS) (SIS), comprise vinylbenzene-(ethene-butylene)-styrene block copolymer (SEBS) and vinylbenzene-(ethylene-propylene) styrene block copolymer (SEPS) in addition, the diene component in soft section is a hydrogenant here.And, can use styrenic based thermoplastic elastomer with reactive group, such as: with the epoxide modified elastomerics of glycidyl methacrylate, and the elastomerics of the unsaturated link(age) of epoxidation conjugated diolefine.Because the high polarity of reactive group, the elastomerics with reactive group improves the consistency with Resins, epoxy, so, make with Resins, epoxy and mix the blended range widens, simultaneously since reactive group by with the crosslinking reaction of Resins, epoxy.And join in the crosslinking structure, thermotolerance and wet fastness after having guaranteed to solidify improve the adherent reliability thus.The example of epoxidation vinyl benzene based elastomeric comprises Epofriend A1020 (Daicel Chemical Industries, Ltd. produces).In the present invention, also the available heat plastic resin replaces the property elastomerics.Tackiness agent must pass through fluidisation.When the heat pressure adhesive of adhesive film, remove, like this, between bonding on-chip circuit, can obtain good electrical connection.So, the Tg of thermoplastic resin be preferably heat pressure adhesive temperature (for example, from 100-130 ℃) or below.The example of this thermoplastic resin comprises polystyrene resin, acrylic resin, phenoxy resin and combination thereof.
The amount of thermoplastic elastomer or resin is generally the 10-900 weight part, preferred 20-500 weight part, more preferably 30-200 weight part, most preferably 40-100 weight part/100 weight part cationically polymerizable monomers.If this amount is less than 10 weight parts, the film-forming properties of binder composition can reduce, if but this amount surpasses 900 weight parts, binder composition as a whole is reduced in cryogenic flowability, between conductive particle and circuit substrate, form bad contact when bonding, cause increasing resistance or reduce connection reliability, sometimes also reduce bond strength.
Under the situation of cationically polymerizable binder composition, the anisotropic-electroconductive adhesive composition of the present invention or the heat-conductive bonding agent composition that contain said components, for example with the form of adhesive film, film is being placed on the substrate after (bonding in advance), want other substrates of adherent, glue head (bonding at last) heat pressure adhesive to binder composition, bonding thus two substrates by pressing.At cationic polymerisation catalyst is under the situation of the activable cationic polymerisation catalyst of ultraviolet, at least in the end bonding before, must be by the radiation ultraviolet ray, the activated adhesive composition.
Conventional binder composition adherent circuit substrate is especially used in the repairing of substrate, more specifically, separates circuit substrate at interconnecting piece, and the operation of removing adhesive residue on one or two circuit substrate, preferably uses following organic solvent to carry out.The circuit substrate interconnecting piece uses laminator, promptly so-called well heater, and as flatiron, compressor and moisture eliminator heat 5-10 second at 100-180 ℃.In circuit substrate heat, peel off a circuit substrate.Subsequently, strong wiping 30-60 second is wiped away with the moistening cotton of organic solvent (as acetone, toluene or methylethylketone (MEK)) in the circuit substrate surface that separates, and removes adhesive residue.Washing is wiped away with the moistening cotton of organic solvent again in the surface of circuit substrate.At this moment must be noted that: organic solvent is contacted with the adjacent circuit interconnecting piece.
Yet under the situation of using cationically polymerizable binder composition of the present invention, circuit substrate can with an organic solvent not repaired.For example, to to proper temperature, apply the separated power of circuit substrate that makes at 100-250 ℃ of scope internal heating with two circuit substrates of anisotropic-electroconductive adhesive composition heat pressure adhesive of the present invention to them, thus, separate two circuit substrates and do not make circuit substrate badly damaged.Under the anisotropic-electroconductive adhesive composition is retained in situation on the circuit substrate, the residue that still is in heated condition can be cleaned with mechanical means with instrument again, instrument is wooden by (terminal portions at least), paper or polymkeric substance constitute, perhaps by used temperature not melt metal constitute.For the flexible circuit of repairing liquid panel and the interconnecting piece between the glass circuit, can use from the flexible electrical trackside instrument is connected to the method for thermal source (as the thermal compressor head), perhaps, use to be placed on glass circuit on the hot plate and the method for heating circuit.
Another characteristic of cationically polymerizable binder composition of the present invention is: for example, under the situation that forms adhesive film, under the solution state that makes, composition is high stability.Generally, when the cationically polymerizable composition of preparation has highly when reactive, its solution must be operated very carefully, for example, by attemperation, does not cause explosive reaction that solution is solidified thus.Yet composition of the present invention contains a small amount of acid amides, and therefore acid amides, can prevent that solution from solidifying as the resistance polymerizing agent of solution.
Embodiment
Each is to the preparation of different conductive adhesion film
1.0 gram cycloaliphatic epoxy resin (trade(brand)name Cyracure UVR6128, Union Carbide Japan Ltd. produces, epoxy equivalent (weight): 200), 5.0 (Epikote 154 to restrain the novolak Resins, epoxy that contains the Racemic glycidol group, YukaShell Epoxy Ltd. produces, epoxy equivalent (weight): 178), 4.0 gram phenoxy resin (PKHC, Phenoxy AssociatesLtd. produces, the OH equivalent: 284) and shown in the table 1, catalyzer is scheduled to the acid amides of equivalent weight, and (embodiment 1: oleylamide (molecular weight: 281); Embodiment 2: erucicamide (molecular weight 338); Embodiment 3: laurylamide (molecular weight 73); Embodiment 4: positive butyramide (molecular weight 87)), mix with 10 gram methylethylketones, stir the mixture until forming uniform solution.Add conductive particle (by on the divinyl benzene copolymer surface, forming nickel dam, and the particle that obtains of overlapping in the above gold, mean particle size: 5 microns) in the solution, in the end account for 3 volume % in the solid, continue to stir and thoroughly disperse until conductive particle.In addition; 0.060 gram cationic polymerisation catalyst (two (η-1; 3, the 5-Three methyl Benzene) iron (II)-three (trifluoromethyl sulfonyl) methide), 0.009 gram stablizer (N; N-diethyl-meta-aminotoluene); 0.2 (Ltd. produces the gram silane coupling agent for Silane Coupling Agent A187, Nippon Unicar Co.; γ-glycidoxypropyltrime,hoxysilane and 0.6 gram methylethylketone mix, and stir until forming uniform solution.This solution is joined in the dispersion soln for preparing above, then further stir.The dispersion soln of the anisotropic-electroconductive adhesive composition that obtains is like this used the blade coating device.On the polyester film of paint as the siloxane treated of partition, 60 ℃ of dryings 10 minutes, obtain the anisotropic conductive adhesive film, 20 microns of thickness (E1-4) then.
4.0 gram contains bisphenol A type epoxy resin (the Epikote YL980 of glycidyl, the trade(brand)name of Yuka Shell Epoxy Ltd., epoxy equivalent (weight): 189), (Epikote 154 2.0 gram contains glycidyl novolak Resins, epoxy, the trade(brand)name of Yuka Shell Epoxy Ltd., epoxy equivalent (weight): 178) 4.0 gram phenoxy resin (PKHC, PhenoxyAssociates Ltd. produces, the OH equivalent: 284) and shown in the table 2, acid amides (oleylamide (molecular weight: 281)) to the predetermined equivalent weight of catalyzer, mix with 10 gram methylethylketones, stir the mixture until forming homogeneous solution.After this,, obtain the anisotropic conductive adhesive film, 20 microns of thickness (E5 and E6) with top identical mode treatment soln.
In order to compare, except saving acid amides (C1), preparing the anisotropic conductive adhesive film with same way as among the embodiment 1, is that 1 equivalent (C2 and C3) or omission acid amides (C4) prepare the anisotropic conductive adhesive film with same way as among the embodiment 5 except the amount of acid amides being changed into to catalyzer perhaps.
Zhi Bei anisotropic conductive adhesive film (2 millimeters of width like this, 4 centimetres of length) adhere on the sheet glass of 0.7 mm thick with ITO (indium tin oxide) film, at 60 ℃, in 4 seconds of pressure 1.0MPa heat pressure adhesive, peel off shim polyester film (bonding in advance) then.After this, the Kapton and flexible circuit (70 microns of the wire pitch that are distributed in the gold plated copper circuit on this film that will comprise 25 micron thickness, 12 microns of 35 microns of conductor widths and thickness) location, and on the pre-adherent anisotropic conductive adhesive film that is fixed in the above.Use the common heating swaging machine, under such condition (being anisotropic conductive adhesive film part) hot pressing at 180 ℃ with in 2.0MPa heating 8-10 second they, finish circuit thus and connect (main bonding).
The assessment of bond strength
With being cut into 5 millimeters width with ito thin film by the flexible circuit that heat pressure adhesive forms to the sheet glass like this,,, write down their maximum value to become 90 ° direction to draw with the sheet glass that has ito thin film with the speed of 50 mm/min.
Evaluation with DSC (differential scanning calorimeter) exothermal nature
If acid amides too suppresses the polyreaction of epoxy compounds, polyreaction is carried out badly, and in the measurement of DSC, this shows as exothermic peak temperature and raises, or calorific value reduces.So, measure the heat release energy 50-200 ℃ scope, the value that obtains is compared with the situation of no acid amides.When measuring, the rate setting that temperature raises is in 10 ℃/minute.
The evaluation of connection state
With the digital multimeter measurement sheet glass of ito thin film and the connection resistance between the flexible circuit are arranged.
Evaluation result is shown in table 1 and table 2.
Table 1
Embodiment Comparative example
Composition ????E1 ???E2 ???E3 ???E4 ???C1 ????C2 ????C3
?UVR6128 ????1 ???1 ???1 ???1 ???1 ????1 ????1
?Epikote154 ????5 ???5 ???5 ???5 ???5 ????5 ????5
?PKHC ????4 ???4 ???4 ???4 ???4 ????4 ????4
Stablizer ????0.009 ???0.009 ???0.009 ???0.009 ???0.009 ????0.009 ????0.009
Silane coupling agent A187 ????0.2 ???0.2 ???0.2 ???0.2 ???0.2 ????0.2 ????0.2
Cationic polymerisation catalyst ????0.06 ???0.06 ???0.06 ???0.06 ???0.06 ????0.06 ????0.06
Acid amides (to the equivalent of catalyzer) Oleylamide 0.0015 (0.1) Erucicamide 0.0018 (0.1) Laurylamide 0.0011 (0.1) Positive butyramide 0.0005 (0.1) Do not have Oleylamide 0.015 (1) Erucicamide 0.018 (1)
The beginning temperature (℃) ????97 ???100 ???99 ???100 ???102 ????95 ????99
The DSC exothermic peak temperature (℃) ????108 ???108 ???108 ???108 ???105 ????105 ????108
DSC heat release energy (card/gram) ????287 ???298 ???298 ???298 ???299 ????68 ????83
Connect resistance (ohm) ????1.8 ???2.0 ???1.6 ???1.7 ???2.2 ????1.8 ????2.2
Average bond strength (N/m) ????663 ???698 ???707 ???679 ???503 ????586 ????705
Failure mode Interior poly- Interior poly- Interior poly- Interior poly- The ITO interface The ITO interface The ITO interface
Table 2
Embodiment Comparative example
Composition ????E5 ????E6 ????C4
?UVR6128 ????4 ????4 ????4
?Epikote154 ????2 ????2 ????2
?PKHC ????4 ????4 ????4
Stablizer ????0.009 ????0.009 ????0.009
Silane coupling agent A187 ????0.2 ????0.2 ????0.2
Cationic polymerisation catalyst ????0.06 ????0.06 ????0.06
Acid amides (to the catalyzer equivalent) Oleylamide 0.0015 (0.1) Oleylamide 0.0045 (0.3) Do not have
The beginning temperature (℃) ????94 ????101 ????96
DSC exothermic peak temperature (℃) ????122 ????128 ????121
DSC heat release energy (card/gram) ????297 ????292 ????307
Connect resistance (ohm) ????1.5 ????1.6 ????1.6
Average bond strength (N/m) ????690 ????590 ????632
Failure mode Interior poly- Interior poly- The ITO interface
Can obviously find out from top table: in an embodiment of the present invention, compare with not adding acid amides situation (C1), the measurement of differential scanning calorimeter discloses: neither reduce the heat release energy, at exothermic peak temperature also indifference.Confirm thus: add the curing reaction that an amount of acid amides does not influence binder composition.In embodiment and comparative example, it is gratifying connecting resistance and peel adhesion strength, but variant on failure mode.More particularly, in arbitrary comparative example, failure mode is the interfacial failure between ITO surface and the tackiness agent, and in adding an embodiment of an amount of acid amides, failure mode is the cohesive failure of tackiness agent, and it is good to be disclosed in interfacial adhesion.
The effect of invention
As several pages of fronts prove that cationically polymerizable adhesive composition of the present invention has splendid bond property, at the interface bond property between adhesive and adherend especially. And, when bonding with cationically polymerizable adhesive composition of the present invention, when repairing, need not use organic solvent, just can easily remove adhesive from adherend.

Claims (9)

1. cationically polymerizable binder composition, it comprises:
(A) cationically polymerizable monomer, it is selected from epoxy monomer, vinyl ether monomers and composition thereof;
(B) cationic polymerisation catalyst; With
(C) stablizer;
It is characterized in that described stablizer (C) is a kind of acid amides of a kind of following molecular formula (I) expression at least:
In the formula, R 1Be alkyl, or contain one or two unsaturated link(age) and the alkenyl that contains 2-30 carbon atom, each R with 1-30 carbon atom 2Be respectively hydrogen or alkyl with 1-10 carbon atom.
2. cationically polymerizable binder composition as claimed in claim 1 is characterized in that: described acid amides is selected from ethanamide, propionic acid amide, positive butyramide, laurylamide, N,N-dimethylacetamide, oleylamide, erucicamide and composition thereof.
3. cationically polymerizable binder composition as claimed in claim 1 is characterized in that: described acid amides blended amount is the whole binder composition of 0.000005-0.02 weight part/100 weight parts.
4. cationically polymerizable binder composition as claimed in claim 1 is characterized in that: described cationically polymerizable monomer is a cycloaliphatic epoxy resin, contains the Resins, epoxy of Racemic glycidol group or their mixture.
5. cationically polymerizable binder composition as claimed in claim 1 is characterized in that: described cationic polymerisation catalyst is a hot activation type cationic polymerisation catalyst.
6. anisotropic-electroconductive adhesive composition, it comprises each described cationically polymerizable binder composition and conductive particle among the claim 1-5.
7. heat-conductive bonding agent composition, it comprises each described cationically polymerizable binder composition and heat conduction particle among the claim 1-5.
8. anisotropic-electroconductive adhesive composition as claimed in claim 6, it is the form with film.
9. heat-conductive bonding agent composition as claimed in claim 7, it is the form with film.
CN 02817905 2001-09-13 2002-07-19 Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition Expired - Fee Related CN1289621C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001278507A JP2003082318A (en) 2001-09-13 2001-09-13 Cationically polymerizable adhesive composition and anisotropically electroconductive adhesive composition
JP278507/2001 2001-09-13

Publications (2)

Publication Number Publication Date
CN1555405A true CN1555405A (en) 2004-12-15
CN1289621C CN1289621C (en) 2006-12-13

Family

ID=19102864

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 02817905 Expired - Fee Related CN1289621C (en) 2001-09-13 2002-07-19 Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition

Country Status (4)

Country Link
JP (1) JP2003082318A (en)
CN (1) CN1289621C (en)
GB (1) GB2393730B (en)
WO (1) WO2003022949A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11016385B2 (en) 2018-08-21 2021-05-25 Industrial Technology Research Institute Photosensitive adhesive composition, photosensitive conductive adhesive composition, and electronic device containing photosensitive conductive adhesive composition

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2182585B1 (en) * 2003-06-25 2011-08-10 Hitachi Chemical Company, Ltd. Circuit member connecting structure
JP5323310B2 (en) * 2005-11-10 2013-10-23 日立化成株式会社 Connection structure and manufacturing method thereof
JP2011049612A (en) * 2006-01-16 2011-03-10 Hitachi Chem Co Ltd Method of manufacturing solar cell module
JP2007214533A (en) * 2006-01-16 2007-08-23 Hitachi Chem Co Ltd Conductive bonding film and solar cell module
CN101512781B (en) 2006-08-29 2013-01-23 日立化成工业株式会社 Conductive adhesive film and solar cell module
US9123835B2 (en) 2006-10-10 2015-09-01 Hitachi Chemical Company, Ltd. Connected structure and method for manufacture thereof
CN100402620C (en) * 2006-11-13 2008-07-16 浙江理工大学 Method of preparing high performance conductive glue
JP2008135654A (en) 2006-11-29 2008-06-12 Sanyo Electric Co Ltd Solar battery module
JP4564977B2 (en) * 2007-04-05 2010-10-20 東京応化工業株式会社 Photosensitive resin composition, method for producing resist pattern, laminate, and device
JP6047437B2 (en) * 2012-03-30 2016-12-21 積水化学工業株式会社 Conductive material, connection structure, and manufacturing method of connection structure
CN102719199A (en) * 2012-04-23 2012-10-10 苏州异导光电材料科技有限公司 Preparation method of three-dimensional anisotropic conductive film
KR102055031B1 (en) * 2012-06-29 2019-12-11 타츠타 전선 주식회사 Conductive adhesive composition, conductive adhesive film, bonding method, and circuit board
KR101706818B1 (en) * 2014-04-30 2017-02-15 제일모직주식회사 A composition for use of anisotropic conductive film, anisotropic conductive film, and semiconductor device
KR101712703B1 (en) * 2014-07-18 2017-03-06 삼성에스디아이 주식회사 Adhesive composition, anisotropic conductive film and the semiconductor device using thereof
KR101706821B1 (en) * 2014-09-01 2017-02-14 삼성에스디아이 주식회사 An anisotropic conductive film and a semi-conductive device connected by the film
JP7013638B2 (en) * 2016-05-31 2022-02-01 昭和電工マテリアルズ株式会社 Adhesive composition and film-like adhesive composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3386955A (en) * 1966-01-14 1968-06-04 American Cyanamid Co Substituted ureas as low temperature epoxy curing agents
DE3508601A1 (en) * 1985-03-11 1986-09-11 Dynamit Nobel Ag, 5210 Troisdorf Metal foil having an adhesive-agent coating for base materials for printed circuits, and a method for producing the base material
DE3666442D1 (en) * 1985-04-02 1989-11-23 Ciba Geigy Ag Curable compositions
JPH05262815A (en) * 1992-03-18 1993-10-12 Nippon Oil & Fats Co Ltd Reactive composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11016385B2 (en) 2018-08-21 2021-05-25 Industrial Technology Research Institute Photosensitive adhesive composition, photosensitive conductive adhesive composition, and electronic device containing photosensitive conductive adhesive composition

Also Published As

Publication number Publication date
GB0403011D0 (en) 2004-03-17
JP2003082318A (en) 2003-03-19
GB2393730A (en) 2004-04-07
CN1289621C (en) 2006-12-13
WO2003022949A1 (en) 2003-03-20
GB2393730B (en) 2005-05-18

Similar Documents

Publication Publication Date Title
CN1289621C (en) Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition
CN1312246C (en) Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition
CN1250663C (en) Anisotropic conductive adhesives having enhanced viscosity and bondng methods and integrated circuit packages using same
CN1243810C (en) Ultraviolet activatable adhesive film
JP6364191B2 (en) Conductive material, connection structure, and manufacturing method of connection structure
KR20050014749A (en) Thermal Interface Material
CN1252204C (en) Method for adhering substrates using light activatable adhesive film
JP6672837B2 (en) Anisotropic conductive adhesive composition, film adhesive, connection structure, and semiconductor device
CN101077956A (en) Welding resistant agent composition for flexible substrate, flexible substrate and preparation method for the flexible substrate
JP6114557B2 (en) Conductive material and connection structure manufacturing method
EP1272586B1 (en) Anisotropically conductive adhesive composition and anisotropically conductive adhesive film formed from it
JP2012171980A (en) Adhesive composition, circuit-connecting material, connected body, method for producing the same and semiconductor device
CN107735477A (en) Conductive adhesive, conductive structure and electronic unit
CN1105749C (en) Conductive epoxy resin compositions anisotropically conductive adhesive films and electrical connecting methods
CN1516727A (en) Method for adhering substrates using ultraviolet activatable adhesive film and ultraviolet irradiation apparatus
JP2004155957A (en) Anisotropic conductive adhesive and film
KR20150005618A (en) Circuit connection material, and manufacturing method for assembly using same
JP6518100B2 (en) PHOTO-CURABLE CONDUCTIVE MATERIAL, CONNECTION STRUCTURE, AND METHOD FOR MANUFACTURING CONNECTION STRUCTURE
US20040266913A1 (en) Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition
JP6518101B2 (en) PHOTO-CURABLE CONDUCTIVE MATERIAL, CONNECTION STRUCTURE, AND METHOD FOR MANUFACTURING CONNECTION STRUCTURE
KR100934553B1 (en) Method for producing an anisotropic conductive film and an anisotropic conductive film produced thereby
CN111484820B (en) Photocurable adhesive composition and photocurable adhesive tape
CN1246412C (en) Flexible printing circuit board adhesive
JP6074215B2 (en) Method for manufacturing organic electroluminescence display element
KR102413834B1 (en) Reworkable conductive adhesive and solar cell module

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee