WO2015019414A1 - Electronic component joint material - Google Patents

Electronic component joint material Download PDF

Info

Publication number
WO2015019414A1
WO2015019414A1 PCT/JP2013/071227 JP2013071227W WO2015019414A1 WO 2015019414 A1 WO2015019414 A1 WO 2015019414A1 JP 2013071227 W JP2013071227 W JP 2013071227W WO 2015019414 A1 WO2015019414 A1 WO 2015019414A1
Authority
WO
WIPO (PCT)
Prior art keywords
curing
electronic component
bonding material
curable resin
resin
Prior art date
Application number
PCT/JP2013/071227
Other languages
French (fr)
Japanese (ja)
Inventor
巧 能見
敏夫 溝脇
博晶 井関
素基 興梠
Original Assignee
千住金属工業株式会社
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 千住金属工業株式会社 filed Critical 千住金属工業株式会社
Priority to PCT/JP2013/071227 priority Critical patent/WO2015019414A1/en
Priority to TW103125958A priority patent/TW201522567A/en
Publication of WO2015019414A1 publication Critical patent/WO2015019414A1/en

Links

Images

Classifications

    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • H01L2224/29309—Indium [In] 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
    • H01L2224/29301—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
    • H01L2224/29338—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
    • H01L2224/29339—Silver [Ag] 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
    • H01L2224/29363—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
    • H01L2224/29393—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
    • H01L2224/28—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
    • H01L2224/29499—Shape or distribution of the fillers
    • 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

Definitions

  • the present invention relates to an electronic component bonding material comprising a conductive adhesive containing carbon nanotubes (carbon nanotubes include a carbon allotrope or a composite of carbon nanotubes and carbon allotrope; substantially CNT).
  • Solder is frequently used as a bonding material for bonding various electronic circuits to a circuit board.
  • lead-free solder such as Sn-Ag-Cu is used as the solder material, but this solder has a higher liquidus temperature of 217 ° C or higher than conventional lead-containing solder.
  • the furnace temperature of the reflow furnace is further higher than the liquidus temperature (260 ° C. or higher), so that a high thermal shock (thermal stress) is applied to the electronic components and circuit boards to be joined.
  • Patent Documents 1 to 4 In order to alleviate this high thermal shock, it is necessary to lower the temperature required for joining, and recently, electronic component joining materials using conductive adhesives have been studied as an alternative to the above solder (cream solder).
  • Patent Document 1 relates to a conductive resin paste containing silver Ag and CNT
  • Patent Document 2 relates to a conductive resin paste containing a thermosetting resin, a curing agent, a metal, and a viscosity modifier in which CNT is dispersed
  • Patent Document 3 is a printed circuit board using a conductive paste, in which a metal and CNT are used as the conductive paste
  • Patent Document 4 is a thermosetting resin containing CNT.
  • the present invention relates to a conductive paste in which conductive particles are kneaded.
  • CNT is highly cohesive
  • the diameter and length of CNT are on the nanometer level
  • the invention disclosed in Patent Document 4 Is characterized by using carbon nanohorns, but carbon nanohorns have a very strong cohesive force compared to multi-walled CNTs, and when dispersed in a resin, they form a sea urchin-like lump. Therefore, there is a dislike that mixing and kneading into a resin becomes difficult and it becomes difficult to finish it into a paste.
  • the present invention solves such a conventional problem, is capable of low-temperature bonding, has sufficient conductive properties and mechanical bonding strength, is inexpensive, and has conductivity that contains CNT instead of paste solder.
  • An electronic component bonding material comprising an adhesive has been invented.
  • the electronic component bonding material according to claim 1 comprises a binder obtained by adding a curing agent and a curing accelerator to a flexible curable resin in which CNTs are dispersed, and conductive particles (such as a metal filler). The conductive particles are mixed and kneaded with the binder to form a paste.
  • tin is preferably used as the conductive particles, and a thermosetting resin having flexibility is used.
  • an acid anhydride is preferably selected as the curing agent, and an organic acid is preferably selected as the curing accelerator.
  • the electronic component bonding material according to claim 4 uses an acid anhydride as a curing agent and an organic acid as a curing accelerator. In electronic component mounting, a very short time of 3 minutes is required as a preferable condition, but the product when the organic acid and the metal material of conductive particles react during resin curing is cured in a short time. It came to know that it contributes greatly to.
  • the balance is preferably a binder with respect to 88 to 90% by mass of the conductive particles.
  • the electronic component bonding material according to claim 6 uses a flexible epoxy resin for a curable resin that constitutes a binder, and when the total amount of the binder is 100% by mass, the resin is 5 to 50% by mass.
  • the CNT used preferably in an amount of 30 to 40% by mass and dispersed in a curable resin having flexibility is 0.1 to 0.1% with respect to 100% by mass when the total amount of the binder is 100% by mass.
  • the curing agent Used in an amount of 10% by mass, preferably less than 3% by mass, and the curing agent is preferably a ratio of succinic acid anhydride to a molar equivalent of 2 (molar ratio of 2 or more) with respect to the flexible curable resin.
  • 2 to 4% by mass of glutaric acid was used as an organic acid which was blended in (1) and was a curing accelerator.
  • the binder is composed of a flexible curable resin, a curing agent, a curing accelerator, and CNTs.
  • the conductive particles are preferably selected in the range of 88 to 90% by mass, and sufficient conductivity (high conductivity) is obtained by close bonding of the conductive particles (tin, etc.) due to the curing of the resin by the curing accelerator in the presence of CNT. Is obtained.
  • the acid anhydride is a curing agent for epoxy resin, but further preferably uses tin as the conductive particles, and the organic acid is used as a curing accelerator, the curing is accelerated, and the curing time and the curing temperature are also reduced. (Curing sufficiently at about 200 ° C. for 3 minutes).
  • the thixotropy (viscosity characteristics) of the paste can be improved, and a value close to that of a conventional solder paste can be realized.
  • an electronic component bonding material can be realized in place of cream solder.
  • the electronic component bonding material according to any one of claims 1 to 6 has sufficient flexibility in terms of electronic component bonding quality.
  • the electronic component bonding material according to claim 7 is provided with flexibility required for electronic component bonding. It was developed to prevent peeling and cracking of electronic component joints when electronic devices are dropped.
  • the electronic component bonding material according to claim 8 has a curable resin that is remelted in a thermal environment higher than the bonding temperature. This makes it possible to repair (repair) after joining the electronic components.
  • An electronic component bonding material comprises a binder in which a curing agent and a curing accelerator are added to a flexible curable resin in which CNTs are dispersed, and conductive particles.
  • the conductive particles are mixed into the binder.
  • the paste is kneaded. As a result, low-temperature bonding is possible, sufficient conductive properties and mechanical bonding strength can be obtained, and an electronic component bonding material using a conductive adhesive containing CNT can be realized at low cost instead of paste solder.
  • the electronic component bonding material according to the present invention is a bonding material that replaces paste solder used when mounting various electronic components on a circuit board or the like, and is cured into a flexible curable resin in which CNTs are dispersed. It consists of a binder to which an agent and a curing accelerator are added, and conductive particles (such as a metal filler). The conductive particles are mixed and kneaded with a binder to form a paste. Then, the composition member of this electronic component joining material is demonstrated.
  • Conductive particles As conductive particles for obtaining conductivity, silver Ag, tin Sn, copper Cu, gold Au, indium In, nickel Ni, palladium Pa, and a group composed of the above-described mixtures.
  • Conductive particles As conductive particles for obtaining conductivity, silver Ag, tin Sn, copper Cu, gold Au, indium In, nickel Ni, palladium Pa, and a group composed of the above-described mixtures
  • One or more selected multi-particle mixtures or alloys are contemplated.
  • suitable conductive particles are selected in consideration of the conductivity and the curing time of the binder.
  • the shape of the conductive particles is not limited. From various shapes such as a spherical shape, a scale shape, a plate shape, a branch shape, a rod shape, a foil shape, and a needle shape, the shape that most improves the conductivity is selected. In this example, a spherical shape was used.
  • FIG. 1 shows experimental data showing that the curing time varies depending on the metal.
  • the composition of the other bonding materials (the binder component shown in FIG. 4) is the same.
  • the cure temperature was measured by differential scanning calorimetry (DSC).
  • the fastest conductive particles were tin, and the curing temperature was 204.4 ° C.
  • Cu (254.85 ° C.) and Ni (279.6 ° C.) were used in this order. Since it is preferable for the bonding material to have a curing time as short as possible, it can be said that the most suitable metal for the conductive particles is tin. Since tin has a melting point of 232 ° C., it is easily melted by being reheated after being cured and bonded once, so that reconnection by repair (repair) is possible.
  • the cured resin is remelted when heated to a temperature higher than the bonding temperature, thereby improving the repairability.
  • FIG. 2 is experimental data showing the relationship of conductivity after resin curing when the above-described three kinds of metals are used as the conductive particles.
  • tin has the lowest surface electrical resistance value, and its value is close to 1.0E-1 ( ⁇ ).
  • the conductivity decreased in the order of Ni and Cu, and the values were 2.0E + 2 for Ni and 2.0E + 5 for Cu.
  • FIG. 3 is a characteristic diagram showing the relationship between the content of conductive particles and volume resistivity.
  • the volume resistivity is obtained by (resistance value ⁇ cross-sectional area / length).
  • the unit is ⁇ cm.
  • a resistance value and a volume resistivity were obtained from a sample having a length of 11.5 mm, a width of 1.5 mm, and a thickness of 0.12 mm.
  • the volume resistivity of the bonding material may rapidly decrease.
  • tin is a conductive particle having a fast curing time and excellent conductivity.
  • the curable resin is the main component of the binder.
  • a curable resin having flexibility is used.
  • the curable resin is selected from resins that are cured by heat, light, ultraviolet rays, or the like.
  • an epoxy resin an epoxy resin, a phenol resin, a polyimide resin, a silicone resin, a polyurethane resin, an unsaturated polyester resin, and the like can be considered, and a resin that is particularly suitable for the screen printing method is selected.
  • the most frequently used curable resin in the electronic equipment industry is a thermosetting resin such as an epoxy resin. Therefore, also in this example, an epoxy resin was used as the curable resin.
  • Epoxy resins are said to be brittle and have poor drop impact properties, while having good electrical and mechanical bonding properties. This is because, when the epoxy resin is completely cured, peeling occurs at the electrode interface even with a weak impact, and cracks occur.
  • flexibility was imparted to the epoxy resin as the main agent. Specifically, for example, by adding an aliphatic skeleton to the epoxy resin, both flexibility and toughness are strengthened, and generation of cracks due to surface peeling is prevented.
  • FIG. 4 is a table showing the overall characteristics of the electronic component bonding material according to the present invention.
  • the resin labeled “flexible resin” in this table is a flexible material having flexibility and toughness. It is an epoxy resin having properties.
  • a general epoxy resin indicated as standard resin
  • Comparative Examples 5 and 6 could not withstand the drop impact and was dropped once. The joint was broken by the impact.
  • the number of breaks (the number of times until breakage) with respect to a drop impact was 100 or more.
  • the curable resin having flexibility is a curable resin having sufficient drop impact characteristics.
  • This drop impact test is a case where a binder and conductive particles made of components as shown in FIG. 4 are used.
  • the drop impact test was performed using the following evaluation substrate.
  • the prepared sample is printed and supplied to the module substrate, and a 12 ⁇ 12 mm size LGA is mounted on the sample substrate to prepare an evaluation substrate. Next, both ends of the substrate are fixed using a dedicated jig at a position where the evaluation substrate is lifted 10 mm from the pedestal.
  • a bisphenol A type epoxy resin was used in an epoxy resin as shown in FIG. 4, and this was given an aliphatic skeleton.
  • EPICLON EXA-4816 manufactured by DIC
  • bisphenol type such as bisphenol A type, bisphenol F type, and bisphenol AP type
  • bisphenols other than bisphenol A type can be applied.
  • Curing agent and curing accelerator Generally, a curing agent is used to accelerate the curing of the epoxy resin. Since the curing agent also functions as a catalyst that improves conduction by contact between the tin particles, which are conductive particles, as a factor that affects the surface electrical resistance value of the bonding material, in addition to the above-described conductive particles, curing can be performed. An agent or a curing accelerator can be considered.
  • An acid anhydride or the like can be used as the curing agent.
  • an amine or the like is used as a curing agent, the curing rate is too high, so an acid anhydride that reacts relatively slowly, such as a succinic acid anhydride, is used.
  • a succinic acid anhydride is used as a curing agent, the curing reaction is too slow and a practical problem occurs. Therefore, it is necessary to promote curing. This is because, in particular, when the joining material is used as a substitute for solder, it is preferable that the curing time be as fast as possible.
  • an organic acid is used as a curing accelerator.
  • the organic acid it is particularly preferable to use glutaric acid which is a kind of carboxylic acid.
  • glutaric acid which is a kind of carboxylic acid.
  • the temperature when curing is as low as possible. This is to shorten the bonding work time and avoid thermal stress on the electronic circuit.
  • the molar ratio of the epoxy resin and the curing agent is preferably (1: 2).
  • FIG. 6 is a characteristic diagram showing an example of this, and when the concentration of glutaric acid is increased to 2% by mass, the surface electrical resistance value ( ⁇ ) tends to decrease remarkably. It is considered that this is because the hardening is promoted by glutaric acid, and the tin particles come into close contact with each other by the hardening, so that the surface electric resistance value is lowered.
  • FIG. 12A is a surface SEM photograph when the finished product is heat-cured, and is a SEM photograph when the magnification is 100 times.
  • FIG. 12B is an SEM photograph when the magnification is 500 times, and
  • FIG. 12C is an SEM photograph when the magnification is 1000 times. It can be seen that the tin particles are in close contact with each other due to the interaction between the curing accelerator and the organic acid described later.
  • the organic acid metal salt (glutaric acid-metal salt) generated during heating. Therefore, the organic acid metal salt generated during heating functions also as a curing accelerator during resin curing.
  • the curing temperature at the peak also differs depending on the concentration of glutaric acid.
  • concentration of glutaric acid is about 2% by mass
  • the temperature is lowered from 216 ° C. to 14 ° C. compared to 0.5% by mass, and is reduced to about 200 ° C.
  • FIG. 8 shows how the time required for the flexible curable resin to completely cure is affected by the presence or absence of a curing agent and the presence or absence of an organic acid metal salt with respect to the flexible curable resin.
  • glutaric acid-Sn salt organic The acid metal salt
  • glutaric acid-Sn salt organic The acid metal salt
  • FIG. 9 is a characteristic diagram showing the transition of the surface electrical resistance value depending on the curing time of the curable resin and the addition amount of glutaric acid.
  • the surface electrical resistance value gradually decreases as the curing time becomes longer, and the surface electrical resistance value tends to be lower when the content of glutaric acid is 4% by mass than 2% by mass.
  • the concentration of glutaric acid is preferably about 2 to 4% by mass.
  • the mass% used in the description of FIGS. 5 to 9 represents the amount of each component when the total amount of the binder is 100% by weight as shown in FIG.
  • a binder is comprised with CNT which is curable resin, a hardening
  • CNT curable resin
  • curing agent a hardening accelerator
  • a carbon allotrope a curable resin obtained by shearing and dispersing CNT is used.
  • CNT functions as a thixotropic agent (thixotropic agent).
  • the viscosity characteristics of the binder are influenced by whether or not CNT is contained in the binder.
  • FIG. 10 shows this viscosity characteristic.
  • Curve Sa is the viscosity characteristic of paste solder in which tin powder is mixed with a binder containing CNT
  • curve Sb is the viscosity characteristic of the binder when CNT is not included.
  • the curve Sc is the viscosity characteristic of the binder containing CNTs.
  • Viscosity is measured when a rotary type is used. As is apparent from the curve Sc, 30 Pa ⁇ s (Pascal ⁇ second) is obtained at 10 rpm viscosity, and about 20 Pa ⁇ s is obtained at 30 rpm viscosity. As shown in FIG. 11, the thixo ratio at that time has a value of about 0.88 at a viscosity of 10 rpm. Compared with the result with a binder not containing CNT, CNT has the effect of simultaneously increasing the viscosity of the binder and the thixo ratio. I understand that I have it.
  • the paste-like solder containing CNT has a viscosity of 170 Pa ⁇ s and a thixo ratio of 0.65.
  • a good viscosity is 150 Pa ⁇ s at 10 rpm viscosity and the thixo ratio is 0.1. Since it is said to be 5 to 0.7, CNT has the effect of giving viscosity characteristics comparable to paste solder.
  • CNTs When CNTs are dispersed in a binder, they are not heated and dissolved, so that a very small amount of CNTs can prevent heating of the bonding material and improve the thixotropy required for printing supply. Thus, it has been found that good viscosity characteristics and a thixo ratio can be realized by dispersing CNTs in a binder which is a curable resin.
  • CNT includes a carbon allotrope or a composite of CNT and carbon allotrope, and is composed of a nanometer-order graphite-based six-membered ring (some of which may be mixed with a five-membered ring, etc.). It is a substance having a structure in which a sheet is formed in a tube shape.
  • CNTs exhibit tremendous performance in terms of conductivity, strength, and thermal conductivity. If they can be entangled with other substances (for example, metal particles), the performance will be greatly improved.
  • CNT is a cylindrical six-membered ring carbon material having a size system of about 0.4 to 100 nm and a length of several ⁇ m.
  • CNTs were used in this example from single-walled CNTs, double-walled CNTs, and multilayered CNTs. CNTs having a fiber diameter of 5 to 80 nm, preferably 8 to 40 nm are used. A fiber length of 0.1 to 3 ⁇ m is used in consideration of dispersibility in a cured resin.
  • the dispersion amount of CNT is 0.1 to 10% by mass, preferably less than 3% by mass when the total amount of binder is 100% by mass, and the most preferable dispersion amount is 1% by mass.
  • the amount of dispersion is large, the cohesiveness becomes strong and the paste is not formed.
  • CNT is exemplified as the carbon allotrope, but other carbon allotropes such as carbon black can be used together.
  • (5) Repair of electronic components Electronic component bonding materials always require electronic component replacement and joint repair in the manufacturing process of the electronic component mounting board. Therefore, it is preferable that the electronic component bonding material once bonded and hardened can be easily removed.
  • the composition components of the bonding material are as shown in FIG. i)
  • the conductive particles (metal filler) are tin powder having a particle size of 25 to 45 ⁇ m.
  • the binder component comprises a curable resin as a main agent, a curing agent, an organic acid, and CNT.
  • the curable resin is a flexible bisphenol-based epoxy resin.
  • the acid anhydride as the curing agent is a succinic acid anhydride.
  • the molar ratio of the epoxy resin and the curing agent is (1: 2).
  • As the CNT a multilayer CNT is used.
  • An electronic component bonding material was prepared by blending tin as a metal filler in an amount of 88% by mass and the binder being the remaining 12% by mass.
  • the mass% of glutaric acid and CNT shown in FIG. 4 is a value when the remaining 12 mass% is 100 mass% in total.
  • the manufacturing process for preparing these is as follows. (1) Create a base material in which CNTs are dispersed in a curable resin. (2) Prepare a dilute solution containing a curable resin, a curing agent, and a curing accelerator. (3) Mix the base material of (1) and the diluted solution of (2), and mix the conductive particles. (A) About Comparative Examples 5 and 6 Comparative Examples 5 and 6 are cases where an ordinary resin (standard resin) that is not given flexibility is used as the curable resin.
  • Comparative Examples 1 to 3 use a curable resin having the same flexibility as that of the present invention as the curable resin, and the molar ratio of the epoxy resin to the curing agent is (1: 1). This is the case when it is selected as the equivalent mole. Comparative Examples 2 and 3 were selected such that the molar ratio of the epoxy resin and the curing agent was (1: 1), and the CNTs were increased to contain 3% by mass and 5% by mass, respectively.
  • the volume resistivity is infinite and the viscosity becomes too high for any of the volume resistivity, viscosity, and thixo ratio, and the viscosity measurement becomes impossible, which is out of the question. It was. Therefore, the CNT must be less than 3% by mass.
  • the comparative example 1 is a case where 1 mass% of CNT is contained. In this case, although it was in a completely cured state in a curing experiment at 200 ° C. for 3 minutes, the molar ratio of the epoxy resin and the curing agent was (1: 1), resulting in a very high volume resistivity.
  • Comparative Example 4 uses a curable resin having flexibility and is selected so that the molar ratio of the epoxy resin and the curing agent is (1: 2). And 0% by mass without adding CNTs, the volume resistivity was so high that it could not be measured, and it was uncured even in a curing experiment at 200 ° C. for 3 minutes.
  • Example 1 a curable resin having flexibility is used, and the molar ratio of the epoxy-based resin and the curing agent is selected to be (1: 2). In Example 2, 2% by mass of glutaric acid and 4% by mass of Example 1 are contained.
  • the bonding material is composed of 88 to 90% by mass of tin, which is conductive particles, and the remainder is a binder, and among the binder, a curable resin is a flexible epoxy.
  • a resin, an acid anhydride is used as a curing agent, the molar ratio of the epoxy resin and the curing agent is 1% by mass, the organic acid glutaric acid is 2 to 4% by mass,
  • the composition of glutaric acid, CNT, etc. was adjusted to an appropriate value so as to be 1% by mass, starting from volume resistivity, drop impact characteristics, curing characteristics at 200 ° C. for 3 minutes, sagging by heating, Viscosity and thixo ratio were the expected values.
  • the use of tin as the conductive particles enables high conductivity and low temperature curing, and the use of a flexible curable resin can provide flexibility and toughness.
  • Impact characteristics are greatly improved, and the molar ratio of epoxy resin to curing agent is selected as (1: 2) and glutaric acid is added to add coexistence with tin, shortening the curing time and rapid curing speed.
  • the molar ratio of the epoxy resin and the curing agent is selected as (1: 2) and mixing the organic acid, the volume resistivity decreases.
  • the present invention can be used as a bonding material used when mounting various electronic components and the like on a circuit board, and can also be used as a circuit board component, an electromagnetic shielding material, and a circuit forming material for photovoltaic power generation.

Abstract

The present invention mainly addresses the problem of producing an electronic component joint material which can be cured at a low temperature and contains CNTs that can achieve high electrical conductivity. According to the present invention, an electronic component joint material can be produced using a curable resin having flexibility by dispersing and developing carbon nanotubes in the resin and adding an acid anhydride as a curing agent, an organic acid as a curing accelerator and electrically conductive particles to the resin properly.

Description

電子部品接合材料Electronic component bonding materials
　この発明は、カーボンナノチューブ（カーボンナノチューブには、炭素同素体単体またはカーボンナノチューブと炭素同素体の複合物を含む；略ＣＮＴ）を含有した導電性接着剤からなる電子部品接合材料に関する。 The present invention relates to an electronic component bonding material comprising a conductive adhesive containing carbon nanotubes (carbon nanotubes include a carbon allotrope or a composite of carbon nanotubes and carbon allotrope; substantially CNT).
　回路基板に各種電子回路を接合する接合材料としてはんだが多用されている。
はんだ材料としては環境への影響を考慮して、Ｓｎ－Ａｇ－Ｃｕなどの鉛フリーはんだが使用されているが、このはんだは、従来の鉛入りはんだに比べ液相温度が２１７℃以上と高い。したがって、リフロー炉の炉内温度は液相温度よりもさらに高くなる（２６０℃以上）ため、接合すべき電子部品や回路基板に高い熱衝撃（熱ストレス）を与えてしまう。 Solder is frequently used as a bonding material for bonding various electronic circuits to a circuit board.
In consideration of the impact on the environment, lead-free solder such as Sn-Ag-Cu is used as the solder material, but this solder has a higher liquidus temperature of 217 ° C or higher than conventional lead-containing solder. . Accordingly, the furnace temperature of the reflow furnace is further higher than the liquidus temperature (260 ° C. or higher), so that a high thermal shock (thermal stress) is applied to the electronic components and circuit boards to be joined.
　この高い熱衝撃を緩和するためには、接合に要する温度を低温化させる必要があり、最近では上記はんだ（クリームはんだ）に代わるものとして導電性接着剤を使用した電子部品接合材料が研究されている（特許文献１～４）。 In order to alleviate this high thermal shock, it is necessary to lower the temperature required for joining, and recently, electronic component joining materials using conductive adhesives have been studied as an alternative to the above solder (cream solder). (Patent Documents 1 to 4).
　特許文献１は、銀ＡｇとＣＮＴを含む導電性樹脂ペーストに関するものであり、特許文献２は、ＣＮＴを分散させた熱硬化性樹脂、硬化剤、金属および粘度調整剤を含む導電性樹脂ペーストに関するものであり、特許文献３は導電性ペーストを用いた印刷回路基板であって、導電性ペーストとしては金属とＣＮＴが使用されたものであり、さらに特許文献４は、ＣＮＴを含む熱硬化性樹脂に導電性粒子を混練させた導電性ペーストに関するものである。 Patent Document 1 relates to a conductive resin paste containing silver Ag and CNT, and Patent Document 2 relates to a conductive resin paste containing a thermosetting resin, a curing agent, a metal, and a viscosity modifier in which CNT is dispersed. Patent Document 3 is a printed circuit board using a conductive paste, in which a metal and CNT are used as the conductive paste, and Patent Document 4 is a thermosetting resin containing CNT. The present invention relates to a conductive paste in which conductive particles are kneaded.
特開２００６－１２０６６５号公報JP 2006-120665 A 特開２００８－２９３８２１号公報JP 2008-293821A 特開２００９－１１７３４０号公報JP 2009-117340 A 特開２０１２－７９６８２号公報JP 2012-79682 A
　特許文献１に開示された技術では、熱硬化性樹脂と銀によって導電性を確保しているが、所期の導電効果が得られず導電性が悪いと言う問題がある。
特許文献２に開示された技術では、ＣＮＴの凝集性が妨げとなって、ＣＮＴを樹脂に効率よく分散させることが難しく、結果として目的とする導電性ペーストを得ることが難しいと考えられる。 In the technique disclosed in Patent Document 1, the conductivity is secured by the thermosetting resin and silver, but there is a problem that the intended conductivity effect cannot be obtained and the conductivity is poor.
In the technique disclosed in Patent Document 2, it is considered that CNT aggregation is hindered, and it is difficult to efficiently disperse CNTs in a resin, and as a result, it is difficult to obtain a target conductive paste.
　特許文献３に開示された技術では、ＣＮＴは凝集性が強く、またＣＮＴの径および長さはナノメータレベルであり、ＣＮＴに金属をコーティングする困難性があり、また特許文献４に開示された発明では、カーボンナノホーンを使用していることを特徴としているが、カーボンナノホーンは多層のＣＮＴに比べ、大変強い凝集力を持っており、樹脂に分散させるとウニ状の塊となる。そのため樹脂への混合混練が難しくなり、ペースト状に仕上げるのが難しくなる嫌いがある。 In the technique disclosed in Patent Document 3, CNT is highly cohesive, the diameter and length of CNT are on the nanometer level, and there is a difficulty in coating CNT with metal, and the invention disclosed in Patent Document 4 Is characterized by using carbon nanohorns, but carbon nanohorns have a very strong cohesive force compared to multi-walled CNTs, and when dispersed in a resin, they form a sea urchin-like lump. Therefore, there is a dislike that mixing and kneading into a resin becomes difficult and it becomes difficult to finish it into a paste.
　この発明はこのような従来の課題を解決したものであって、低温接合が可能で、十分な導電特性と機械的接合強度も得られ、安価で、ペーストはんだに代わる、ＣＮＴを含有した導電性接着剤からなる電子部品接合材料を発明した。 The present invention solves such a conventional problem, is capable of low-temperature bonding, has sufficient conductive properties and mechanical bonding strength, is inexpensive, and has conductivity that contains CNT instead of paste solder. An electronic component bonding material comprising an adhesive has been invented.
　上述の課題を解決するため以下のような手段を採用した。なお、後述する実施形態は本発明を実施するために技術的な好ましい条件の例示であるから、これら例示列挙によって発明の範囲が限定されるものではない。
請求項１記載の電子部品接合材料は、ＣＮＴを分散させた可撓性を有する硬化性樹脂に硬化剤と硬化促進剤を加えたバインダーと、導電性粒子（金属フィラー他）からなり、この導電性粒子を上記バインダーに混合・混練させてペースト状となしたことを特徴とする。 In order to solve the above-mentioned problems, the following means are adopted. In addition, since embodiment mentioned later is an illustration of technically preferable conditions in order to implement this invention, the range of invention is not limited by these illustration enumeration.
The electronic component bonding material according to claim 1 comprises a binder obtained by adding a curing agent and a curing accelerator to a flexible curable resin in which CNTs are dispersed, and conductive particles (such as a metal filler). The conductive particles are mixed and kneaded with the binder to form a paste.
　請求項２記載の電子部品接合材料は、導電性粒子として好ましくは錫が使用されると共に、可撓性を有する熱硬化型樹脂を使用した。
　請求項３記載の電子部品接合材料は、硬化剤として好ましくは酸無水物を選択し、硬化促進剤として好ましくは有機酸を選択した。　
　請求項４記載の電子部品接合材料は硬化剤としての酸無水物を使用すると共に、硬化促進剤として有機酸を使用した。電子部品実装においては好ましい条件として硬化時間が３分という非常に短い時間が要求されるが、有機酸と導電性粒子の金属素材が樹脂硬化中に反応したときの生成物が短時間での硬化に大きく寄与することを知見するに至った。 In the electronic component bonding material according to the second aspect, tin is preferably used as the conductive particles, and a thermosetting resin having flexibility is used.
In the electronic component bonding material according to claim 3, an acid anhydride is preferably selected as the curing agent, and an organic acid is preferably selected as the curing accelerator.
The electronic component bonding material according to claim 4 uses an acid anhydride as a curing agent and an organic acid as a curing accelerator. In electronic component mounting, a very short time of 3 minutes is required as a preferable condition, but the product when the organic acid and the metal material of conductive particles react during resin curing is cured in a short time. It came to know that it contributes greatly to.
　請求項５記載の電子部品接合材料は、好ましくは導電性粒子８８～９０質量％に対し、残部がバインダーである。　
　請求項６記載の電子部品接合材料は、バインダーを構成する可撓性を有する硬化性樹脂用エポキシ系樹脂が使用され、バインダーの総量を１００質量％としたとき、当該樹脂は５～５０質量％、好ましくは３０～４０質量％使用され、可撓性を有する硬化性樹脂に分散されるＣＮＴは、同じくバインダーの総量を１００質量％としたとき、この１００質量％に対して、０．１～１０質量％、好ましくは３質量％未満で使用され、硬化剤は好ましくはコハク酸系酸無水物が、可撓性を有する硬化性樹脂に対して当モル以上（２以上のモル比）の割合で配合されると共に硬化促進剤である有機酸はグルタル酸を２～４質量％使用した。　
　ここに、バインダーは、可撓性を有する硬化性樹脂と硬化剤、硬化促進剤およびＣＮＴで構成されるものとする。 In the electronic component bonding material according to claim 5, the balance is preferably a binder with respect to 88 to 90% by mass of the conductive particles.
The electronic component bonding material according to claim 6 uses a flexible epoxy resin for a curable resin that constitutes a binder, and when the total amount of the binder is 100% by mass, the resin is 5 to 50% by mass. The CNT used preferably in an amount of 30 to 40% by mass and dispersed in a curable resin having flexibility is 0.1 to 0.1% with respect to 100% by mass when the total amount of the binder is 100% by mass. Used in an amount of 10% by mass, preferably less than 3% by mass, and the curing agent is preferably a ratio of succinic acid anhydride to a molar equivalent of 2 (molar ratio of 2 or more) with respect to the flexible curable resin. In addition, 2 to 4% by mass of glutaric acid was used as an organic acid which was blended in (1) and was a curing accelerator.
Here, the binder is composed of a flexible curable resin, a curing agent, a curing accelerator, and CNTs.
導電性粒子を好ましくは８８～９０質量％を選択すると共に、ＣＮＴ共存化で硬化促進剤による樹脂の硬化によって導電性粒子（錫等）同士の密な結合により十分な導通性（高導電性）が得られる。 The conductive particles are preferably selected in the range of 88 to 90% by mass, and sufficient conductivity (high conductivity) is obtained by close bonding of the conductive particles (tin, etc.) due to the curing of the resin by the curing accelerator in the presence of CNT. Is obtained.
　酸無水物はエポキシ系樹脂の硬化剤であるが、さらに導電性粒子として好ましくは錫を使用し、有機酸を硬化促進剤として使用することで硬化が促進され、硬化時間および硬化温度も低下する（２００℃３分程度で十分硬化する）。 The acid anhydride is a curing agent for epoxy resin, but further preferably uses tin as the conductive particles, and the organic acid is used as a curing accelerator, the curing is accelerated, and the curing time and the curing temperature are also reduced. (Curing sufficiently at about 200 ° C. for 3 minutes).
　可撓性を有する硬化性樹脂にＣＮＴを分散させると共に、その分散量を適宜選定することで、ペーストのチキソ性（粘度特性）を改善でき、従来のソルダーペーストに近い値を実現できる。これによってクリームはんだに代わる電子部品接合材料が実現できる。　
　請求項１から請求項６記載の電子部品接合材料は電子部品接合品質において充分な可撓性が確保されている。 By dispersing CNTs in a curable resin having flexibility and appropriately selecting the amount of dispersion, the thixotropy (viscosity characteristics) of the paste can be improved, and a value close to that of a conventional solder paste can be realized. As a result, an electronic component bonding material can be realized in place of cream solder.
The electronic component bonding material according to any one of claims 1 to 6 has sufficient flexibility in terms of electronic component bonding quality.
　請求項７記載の電子部品接合材料は電子部品接合上必要とされる可撓性を付与したものである。電子機器の落下時における電子部品接合部の剥離やクラックの発生を予防するために開発されたものである。　
　請求項８記載の電子部品接合材料は接合温度より高熱環境下で再溶融する硬化性樹脂を有することを特徴とする。これにより電子部品接合後の修理（リペア）が可能になる。 The electronic component bonding material according to claim 7 is provided with flexibility required for electronic component bonding. It was developed to prevent peeling and cracking of electronic component joints when electronic devices are dropped.
The electronic component bonding material according to claim 8 has a curable resin that is remelted in a thermal environment higher than the bonding temperature. This makes it possible to repair (repair) after joining the electronic components.
　この発明による電子部品接合材料は、ＣＮＴを分散させた可撓性を有する硬化性樹脂に硬化剤と硬化促進剤を加えたバインダーと、導電性粒子からなり、この導電性粒子をバインダーに混合・混練させてペースト状としたものである。これにより低温接合が可能で、十分な導電特性と機械的接合強度が得られ、安価でペーストはんだに代わる、ＣＮＴを含有した導電性接着剤を使用した電子部品接合材料を実現できる。 An electronic component bonding material according to the present invention comprises a binder in which a curing agent and a curing accelerator are added to a flexible curable resin in which CNTs are dispersed, and conductive particles. The conductive particles are mixed into the binder. The paste is kneaded. As a result, low-temperature bonding is possible, sufficient conductive properties and mechanical bonding strength can be obtained, and an electronic component bonding material using a conductive adhesive containing CNT can be realized at low cost instead of paste solder.
　この電子部品接合材料を使用すると、はんだ付けで実施してきた複雑な温度プロファイルの設定が不要となり、大幅な製造タクトの短縮が可能となる。実装工程が簡易になり、専門的技術がなくても実装が可能になる。 If this electronic component bonding material is used, the setting of a complicated temperature profile that has been carried out by soldering becomes unnecessary, and the manufacturing tact time can be greatly reduced. The mounting process is simplified and mounting is possible even without specialized technology.
金属フィラーの種類と硬化温度との関係を示す図である。It is a figure which shows the relationship between the kind of metal filler, and hardening temperature. 金属フィラーの種類と導電性との関係を示す図である。It is a figure which shows the relationship between the kind of metal filler, and electroconductivity. 金属フィラーの含有量と体積抵抗率との関係を示す特性図である。It is a characteristic view which shows the relationship between content of a metal filler, and volume resistivity. この発明に係る電子部品接合材料の総合特性を示す表図である。It is a table | surface figure which shows the comprehensive characteristic of the electronic component joining material which concerns on this invention. エポキシ樹脂と硬化剤との混合比の関係および硬化促進剤と表面電気抵抗値との関係を示す表図である。It is a table | surface figure which shows the relationship between the mixing ratio of an epoxy resin and a hardening | curing agent, and the relationship between a hardening accelerator and a surface electrical resistance value. 硬化促進剤としてのグルタル酸の濃度と導通性との関係を示す特性図である。It is a characteristic view which shows the relationship between the density | concentration of glutaric acid as a hardening accelerator, and electroconductivity. 硬化促進剤としてのグルタル酸の濃度と硬化時間との関係を示す特性図である。It is a characteristic view which shows the relationship between the density | concentration of glutaric acid as a hardening accelerator, and hardening time. グルタル酸と錫が反応して生成する硬化促進剤添加による硬化時間と硬化速度との関係を示す表図である。It is a table | surface figure which shows the relationship between the hardening time by the hardening accelerator addition which a glutaric acid and tin produce | generate, and a hardening rate. 硬化促進剤と硬化時間および表面電気抵抗値の関係を示す特性図である。It is a characteristic view which shows the relationship between a hardening accelerator, hardening time, and a surface electrical resistance value. ＣＮＴを添加することによって、バインダーとペーストの粘性への変化を示す特性図である。It is a characteristic view which shows the change to the viscosity of a binder and a paste by adding CNT. 粘度とチキソ性の関係を示す表図である。It is a table | surface figure which shows the relationship between a viscosity and thixotropy. 完成品を加熱硬化させた時の表面ＳＥＭ写真であって、倍率が１００倍であるときのＳＥＭ写真である。It is a surface SEM photograph when the finished product is heat-cured, and is a SEM photograph when the magnification is 100 times. 完成品を加熱硬化させた時の表面ＳＥＭ写真であって、倍率が５００倍であるときのＳＥＭ写真である。It is a surface SEM photograph when the finished product is heat-cured, and is a SEM photograph when the magnification is 500 times. 完成品を加熱硬化させた時の表面ＳＥＭ写真であって、倍率が１０００倍であるときのＳＥＭ写真である。It is a surface SEM photograph when the finished product is heat-cured, and is a SEM photograph when the magnification is 1000 times.
　本発明を実施するための好ましい形態を以下に説明する。以下に述べる実施例は本発明を実施するために技術的な好ましい例示であって、この例示的列挙によって発明の範囲が限定されるものではない。 Preferred modes for carrying out the present invention will be described below. The following examples are technically preferable examples for carrying out the present invention, and the scope of the invention is not limited by this exemplary list.
　続いて、この発明に係るＣＮＴを含有した電子部品接合材料の一例を以下に説明する。
この発明による電子部品接合材料は、各種電子部品を回路基板などに実装するときに使用されるペースト状はんだに替わる接合材料であって、ＣＮＴを分散させた可撓性を有する硬化性樹脂に硬化剤と硬化促進剤を加えたバインダーと、導電性粒子（金属フィラー等）からなる。　
　この導電性粒子をバインダーに混合・混練させてペースト状にしたものである。続いて、この電子部品接合材料の組成部材について説明する。　
（１）導電性粒子について
　導電性を得るための導電性粒子としては、銀Ａｇ、錫Ｓｎ、銅Ｃｕ、金Ａｕ、インジウムＩｎ、ニッケルＮｉ、パラジウムＰａおよび前記記載の混合物で構成される群より選択された１種または２種以上の複数粒子混合物または合金が考えられる。　 Subsequently, an example of an electronic component bonding material containing CNTs according to the present invention will be described below.
The electronic component bonding material according to the present invention is a bonding material that replaces paste solder used when mounting various electronic components on a circuit board or the like, and is cured into a flexible curable resin in which CNTs are dispersed. It consists of a binder to which an agent and a curing accelerator are added, and conductive particles (such as a metal filler).
The conductive particles are mixed and kneaded with a binder to form a paste. Then, the composition member of this electronic component joining material is demonstrated.
(1) Conductive particles As conductive particles for obtaining conductivity, silver Ag, tin Sn, copper Cu, gold Au, indium In, nickel Ni, palladium Pa, and a group composed of the above-described mixtures One or more selected multi-particle mixtures or alloys are contemplated.
　これらの金属群の中から導電性やバインダーの硬化時間などを考慮して好適な導電性粒子が選択される。導電性粒子の形状は限定されない。球状、鱗片状、板状、枝状、棒状、箔状、針状等種々の形状の中から、最も導電性を向上させる形状が選択されるもので、本例では球状体を用いた。 From these metal groups, suitable conductive particles are selected in consideration of the conductivity and the curing time of the binder. The shape of the conductive particles is not limited. From various shapes such as a spherical shape, a scale shape, a plate shape, a branch shape, a rod shape, a foil shape, and a needle shape, the shape that most improves the conductivity is selected. In this example, a spherical shape was used.
　導電性粒子の種類によって電子部品接合材料が硬化するまでの時間が異なる。
図１は金属によって硬化時間が相違することを示す実験データであって、図１では導電性粒子としてＳｎ，Ｃｕ、Ｎｉの３種を選んで実験した。それ以外の接合材料の組成（図４に示されるバインダー成分）は同一である。硬化温度の測定は示差走査熱量測定（ＤＳＣ）に依った。 The time until the electronic component bonding material is cured varies depending on the type of conductive particles.
FIG. 1 shows experimental data showing that the curing time varies depending on the metal. In FIG. 1, three types of conductive particles, Sn, Cu, and Ni, were selected for the experiment. The composition of the other bonding materials (the binder component shown in FIG. 4) is the same. The cure temperature was measured by differential scanning calorimetry (DSC).
　図１のように、最も早く硬化する導電性粒子は錫であって、硬化温度は２０４．４℃を示した。以下、Ｃｕ（２５４．８５℃）、Ｎｉ（２７９．６℃）の順となった。
接合材料としてはできるだけ硬化時間が短い方が好ましいので、導電性粒子として最も好適な金属は錫であると言える。　
錫は２３２℃の融点を持つため、一度硬化接合した後、再加熱することで容易に溶けるから、修理（リペア）による再接続が可能である。 As shown in FIG. 1, the fastest conductive particles were tin, and the curing temperature was 204.4 ° C. In the following, Cu (254.85 ° C.) and Ni (279.6 ° C.) were used in this order.
Since it is preferable for the bonding material to have a curing time as short as possible, it can be said that the most suitable metal for the conductive particles is tin.
Since tin has a melting point of 232 ° C., it is easily melted by being reheated after being cured and bonded once, so that reconnection by repair (repair) is possible.
併せて、硬化した樹脂は接合温度より高温に加熱した時再溶融し、これによってリペア性が向上する。 In addition, the cured resin is remelted when heated to a temperature higher than the bonding temperature, thereby improving the repairability.
　図２は、導電性粒子として上述した３種類の金属を使用したときの樹脂硬化後における導通性の関係を示す実験データである。
図２より明らかなように、最も表面電気抵抗値が低いのが錫で、その値は１．０Ｅ－１（Ω）に近い値を示した。Ｎｉ，Ｃｕの順に導通性が悪くなり、その値はＮｉが２．０Ｅ＋２で、Ｃｕが２．０Ｅ＋５であった。 FIG. 2 is experimental data showing the relationship of conductivity after resin curing when the above-described three kinds of metals are used as the conductive particles.
As is clear from FIG. 2, tin has the lowest surface electrical resistance value, and its value is close to 1.0E-1 (Ω). The conductivity decreased in the order of Ni and Cu, and the values were 2.0E + 2 for Ni and 2.0E + 5 for Cu.
　図３は、導電性粒子の含有量と体積抵抗率との関係を示す特性図ある。体積抵抗率は、（抵抗値×断面積／長さ）で求まる。単位は、Ωｃｍである。この例では、長さが１１．５ｍｍ、幅が１．５ｍｍ、厚みが０．１２ｍｍの試料から抵抗値と体積抵抗率を求めた。 FIG. 3 is a characteristic diagram showing the relationship between the content of conductive particles and volume resistivity. The volume resistivity is obtained by (resistance value × cross-sectional area / length). The unit is Ωcm. In this example, a resistance value and a volume resistivity were obtained from a sample having a length of 11.5 mm, a width of 1.5 mm, and a thickness of 0.12 mm.
　この図より明らかなように導電性粒子の含有量が接合材料の総量１００質量％に対して８８～９０質量％を占めるように含有させると、接合材料の体積抵抗率が急激に低下することが判る。 As is apparent from this figure, when the conductive particles are contained so that the content of the conductive particles occupies 88 to 90% by mass with respect to the total amount of the bonding material of 100% by mass, the volume resistivity of the bonding material may rapidly decrease. I understand.
含有量が９０質量％になると、体積抵抗率は１．０Ｅ－４（Ω・ｃｍ）まで低下するのではんだに必要な導電性は十分確保できることになる。このように錫は硬化時間が早く、しかも導電性に優れた導電性粒子であることが判った。 When the content is 90% by mass, the volume resistivity decreases to 1.0E-4 (Ω · cm), so that the necessary conductivity for the solder can be sufficiently secured. Thus, it was found that tin is a conductive particle having a fast curing time and excellent conductivity.
　これは後述するように硬化促進剤用の有機酸としてグルタル酸を用いた場合には硬化触媒として大きく寄与すると共に、樹脂硬化中にグルタル酸と錫が反応して（グルタル酸－金属塩）が生成される過程で錫粒子同士の接触を強めるように作用しているものと考えられる。　
同時に有機酸であるグルタル酸によって錫の表面酸化を取り除くように作用しているものと考えられる。これらの相乗・相互作用によって、低温硬化と高導電性を実現した。
（２）バインダーの主剤としての硬化性樹脂について
　バインダーの主剤となるのは硬化性樹脂であって、この発明では可撓性を有する硬化性樹脂が使用される。硬化性樹脂としては熱、光、紫外線等で硬化する樹脂の中から選択される。 As will be described later, when glutaric acid is used as the organic acid for the curing accelerator, it greatly contributes as a curing catalyst, and glutaric acid reacts with tin during curing of the resin (glutaric acid-metal salt). It is thought that it acts to strengthen the contact between the tin particles in the process of generation.
At the same time, it is considered that glutaric acid, which is an organic acid, acts to remove surface oxidation of tin. Through these synergies and interactions, low temperature curing and high electrical conductivity have been realized.
(2) About the curable resin as the main component of the binder The curable resin is the main component of the binder. In the present invention, a curable resin having flexibility is used. The curable resin is selected from resins that are cured by heat, light, ultraviolet rays, or the like.
　硬化性樹脂としてはエポキシ系樹脂、フェノール系樹脂、ポリイミド系樹脂、シリコーン系樹脂、ポリウレタン系樹脂、不飽和ポリエステル樹脂などが考えられるが、特にスクリーン印刷工法に最適な樹脂が選択される。 As the curable resin, an epoxy resin, a phenol resin, a polyimide resin, a silicone resin, a polyurethane resin, an unsaturated polyester resin, and the like can be considered, and a resin that is particularly suitable for the screen printing method is selected.
　電子機器業界で最も多用されている硬化性樹脂としては、エポキシ系樹脂などの熱硬化性樹脂である。したがって本例でもエポキシ系樹脂を硬化性樹脂として使用した。
エポキシ系樹脂は、電気的・機械的接合特性が良好である反面、脆弱で落下衝撃特性が悪いと言われている。エポキシ系樹脂を完全硬化させると弱い衝撃でも電極界面で剥離が起き、クラックが発生するためである。 The most frequently used curable resin in the electronic equipment industry is a thermosetting resin such as an epoxy resin. Therefore, also in this example, an epoxy resin was used as the curable resin.
Epoxy resins are said to be brittle and have poor drop impact properties, while having good electrical and mechanical bonding properties. This is because, when the epoxy resin is completely cured, peeling occurs at the electrode interface even with a weak impact, and cracks occur.
　そのため、この発明では主剤となるエポキシ系樹脂に可撓性を付与した。
具体的にはエポキシ系樹脂に例えば脂肪族骨格を付与することで、柔軟性と強靱性の双方を共に強化し、表面剥離によるクラックの発生を防止するようにした。 Therefore, in this invention, flexibility was imparted to the epoxy resin as the main agent.
Specifically, for example, by adding an aliphatic skeleton to the epoxy resin, both flexibility and toughness are strengthened, and generation of cracks due to surface peeling is prevented.
　図４は、この発明に係る電子部品接合材料の総合特性を示す表図であるが、この表図において「可撓性樹脂」と標記された樹脂が、柔軟性と強靱性を備えた可撓性を有するエポキシ樹脂のことである。
図４からも明らかなように、落下衝撃試験を行ったところ、一般的なエポキシ系樹脂（標準樹脂と表示）（比較例５と６）では、落下衝撃には耐えられず、一回の落下衝撃で接合部が破断してしまった。 FIG. 4 is a table showing the overall characteristics of the electronic component bonding material according to the present invention. The resin labeled “flexible resin” in this table is a flexible material having flexibility and toughness. It is an epoxy resin having properties.
As is apparent from FIG. 4, when a drop impact test was performed, a general epoxy resin (indicated as standard resin) (Comparative Examples 5 and 6) could not withstand the drop impact and was dropped once. The joint was broken by the impact.
　一方、可撓性を有する硬化性樹脂の場合には（実施例１および２）に示すように、何れも落下衝撃に対する破断回数（破断するまでの回数）が１００回以上となった。これによって可撓性を有する硬化性樹脂は十分な落下衝撃特性を持った硬化性樹脂であることが判る。 On the other hand, in the case of a curable resin having flexibility, as shown in (Examples 1 and 2), the number of breaks (the number of times until breakage) with respect to a drop impact was 100 or more. Thus, it can be seen that the curable resin having flexibility is a curable resin having sufficient drop impact characteristics.
　この落下衝撃試験は、図４に示したような成分からなるバインダーと導電性粒子を使用した場合である。落下衝撃試験は次のような評価用基板を使用して行った。
作成した試料をモジュール用基板に印刷供給し、これに１２×１２ｍｍサイズのＬＧＡを搭載して評価用基板を作成する。次に、この評価基板を台座から１０ｍｍ浮かせた位置に専用治具を用いて基板両端を固定する。 This drop impact test is a case where a binder and conductive particles made of components as shown in FIG. 4 are used. The drop impact test was performed using the following evaluation substrate.
The prepared sample is printed and supplied to the module substrate, and a 12 × 12 mm size LGA is mounted on the sample substrate to prepare an evaluation substrate. Next, both ends of the substrate are fixed using a dedicated jig at a position where the evaluation substrate is lifted 10 mm from the pedestal.
　その状態でJEDEC規格に則って加速度１５００Ｇの衝撃を繰り返し与える。そしてＬＧＡがモジュール基板から剥離（離脱）するまでの回数を計測し、これを落下回数として用いた。最初の衝撃で離脱したときは測定不能とした。 In that state, impact of acceleration 1500G is repeatedly applied according to JEDEC standard. Then, the number of times until the LGA peels (detaches) from the module substrate was measured, and this was used as the number of drops. Measurement was impossible when released on the first impact.
　可撓性を有する硬化性樹脂としては、図４にも示したようにエポキシ系樹脂の中でビスフェノールＡ型エポキシ樹脂を使用し、これに脂肪族骨格を持たせた。脂肪族骨格を付与したビスフェノールＡ型エポキシ樹脂としては、EPICLON EXA-4816（DIC社製）などが知られている。 As the flexible curable resin, a bisphenol A type epoxy resin was used in an epoxy resin as shown in FIG. 4, and this was given an aliphatic skeleton. As a bisphenol A type epoxy resin imparted with an aliphatic skeleton, EPICLON EXA-4816 (manufactured by DIC) is known.
　ビスフェノール型には、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＰ型のように沢山のビスフェノール型が知られているので、ビスフェノールＡ型以外のビスフェノールでも適用できることは容易に理解できる。
（３）硬化剤と硬化促進剤について
　一般的にエポキシ系樹脂の硬化を早めるために硬化剤が使用される。
硬化剤は、導電性粒子である錫粒子同士の接触による導通を向上させる触媒としても機能するので、接合材料の表面電気抵抗値に影響を与える因子としては、上述した導電性粒子の他に硬化剤や硬化促進剤が考えられる。 Since many bisphenol types are known as bisphenol type, such as bisphenol A type, bisphenol F type, and bisphenol AP type, it can be easily understood that bisphenols other than bisphenol A type can be applied.
(3) Curing agent and curing accelerator Generally, a curing agent is used to accelerate the curing of the epoxy resin.
Since the curing agent also functions as a catalyst that improves conduction by contact between the tin particles, which are conductive particles, as a factor that affects the surface electrical resistance value of the bonding material, in addition to the above-described conductive particles, curing can be performed. An agent or a curing accelerator can be considered.
　硬化剤としては酸無水物などを使用できる。
硬化剤としてアミン等を使用すると硬化速度が速すぎる嫌いがあるので、コハク酸系酸無水物などのように比較的緩やかに反応する酸無水物が使用される。ただし硬化剤としてコハク酸系酸無水物を使用すると、硬化反応が緩やか過ぎて実用上の問題が発生する。
そのため、硬化の促進を図る必要がある。特に、接合材料をはんだ代用として使用する場合、硬化時間はできるだけ早い方が好ましいからである。 An acid anhydride or the like can be used as the curing agent.
When an amine or the like is used as a curing agent, the curing rate is too high, so an acid anhydride that reacts relatively slowly, such as a succinic acid anhydride, is used. However, when a succinic acid anhydride is used as a curing agent, the curing reaction is too slow and a practical problem occurs.
Therefore, it is necessary to promote curing. This is because, in particular, when the joining material is used as a substitute for solder, it is preferable that the curing time be as fast as possible.
　この発明では硬化促進剤として有機酸が使用されている。
有機酸としては特にカルボン酸の一種であるグルタル酸の使用が好ましい。
接合材料の場合、硬化させる時の温度ができるだけ低い方が好ましい。
接合作業時間を短縮すると共に、電子回路などへの熱的ストレスを避けるためである。 In this invention, an organic acid is used as a curing accelerator.
As the organic acid, it is particularly preferable to use glutaric acid which is a kind of carboxylic acid.
In the case of a bonding material, it is preferable that the temperature when curing is as low as possible.
This is to shorten the bonding work time and avoid thermal stress on the electronic circuit.
　続いて硬化剤と硬化促進剤の関係について説明する。
図５に示すように、一般的エポキシ系樹脂に対して硬化剤が当モルの配合
（１：１）では、硬化促進剤（この例ではグルタル酸）をいくら投入しても導通性は得られない。 Next, the relationship between the curing agent and the curing accelerator will be described.
As shown in FIG. 5, when the curing agent is equimolar (1: 1) to a general epoxy resin, conductivity is obtained no matter how much a curing accelerator (glutaric acid in this example) is added. Absent.
　しかし、一般的エポキシ系樹脂に対して硬化剤を過剰に投入した条件下、例えば（１：２）の割合（モル比）となるように投入した場合で有機酸、中でもグルタル酸が存在すると、図５に示すように表面電気抵抗値（Ω）が小さくなり、導通性が得られることが判った。したがって、エポキシ系樹脂と硬化剤とのモル比は（１：２）が好適である。 However, under conditions in which a curing agent is excessively added to a general epoxy resin, for example, when an organic acid, particularly glutaric acid, is present in a ratio (molar ratio) of (1: 2), As shown in FIG. 5, it was found that the surface electrical resistance value (Ω) was reduced and electrical conductivity was obtained. Therefore, the molar ratio of the epoxy resin and the curing agent is preferably (1: 2).
　また、有機酸としてグルタル酸を使用した場合、その濃度もある程度濃い方が導通性を改善されることが判った。
図６はその一例を示す特性図であって、グルタル酸の濃度を２質量％まで高めると表面電気抵抗値（Ω）が著しく下がる傾向にある。これはグルタル酸によって硬化が促進され、その硬化によって錫粒子同士が密着して接触するようになるため、表面電気抵抗値が下がるものと考えられる。 Further, it was found that when glutaric acid is used as the organic acid, the conductivity is improved when the concentration is higher to some extent.
FIG. 6 is a characteristic diagram showing an example of this, and when the concentration of glutaric acid is increased to 2% by mass, the surface electrical resistance value (Ω) tends to decrease remarkably. It is considered that this is because the hardening is promoted by glutaric acid, and the tin particles come into close contact with each other by the hardening, so that the surface electric resistance value is lowered.
　加えて、グルタル酸によって錫表面の酸化膜を除去する働きもあるものと考えられる。
図１２Ａは、完成品を加熱硬化させた時の表面ＳＥＭ写真であって、倍率が１００倍であるときのＳＥＭ写真である。図１２Ｂは、同じく倍率が５００倍であるときのＳＥＭ写真であり、図１２Ｃは、倍率が１０００倍であるときのＳＥＭ写真である。硬化促進剤や後述の有機酸の相互作用によって錫粒子同士がより強固に密着した状態で接触していることが判る。 In addition, it is considered that there is a function of removing the oxide film on the tin surface with glutaric acid.
FIG. 12A is a surface SEM photograph when the finished product is heat-cured, and is a SEM photograph when the magnification is 100 times. FIG. 12B is an SEM photograph when the magnification is 500 times, and FIG. 12C is an SEM photograph when the magnification is 1000 times. It can be seen that the tin particles are in close contact with each other due to the interaction between the curing accelerator and the organic acid described later.
グルタル酸は錫と共存することで、加熱中に生成される有機酸金属塩（グルタル酸－金属塩）によって硬化速度が高められると考えられる。したがって、加熱中に生成される有機酸金属塩は、樹脂硬化中において硬化促進剤としても機能していることになる。 When glutaric acid coexists with tin, it is considered that the curing rate is increased by the organic acid metal salt (glutaric acid-metal salt) generated during heating. Therefore, the organic acid metal salt generated during heating functions also as a curing accelerator during resin curing.
　図７のようにグルタル酸の濃度によってもピーク時の硬化温度が相違する。
グルタル酸の濃度が２質量％程度の濃度になると、０．５質量％のときに比べ２１６℃から１４℃も下がり、ほぼ２００℃程度に低下する。 As shown in FIG. 7, the curing temperature at the peak also differs depending on the concentration of glutaric acid.
When the concentration of glutaric acid is about 2% by mass, the temperature is lowered from 216 ° C. to 14 ° C. compared to 0.5% by mass, and is reduced to about 200 ° C.
　したがって錫にグルタル酸が共存すると、硬化速度が高められることが判る。
図８は、可撓性を有する硬化性樹脂に対し、硬化剤の有無および有機酸金属塩の有無によって、可撓性を有する硬化性樹脂が完全硬化する時間がどのように影響するかを示した表図である。 Therefore, it can be seen that when glutaric acid coexists with tin, the curing rate is increased.
FIG. 8 shows how the time required for the flexible curable resin to completely cure is affected by the presence or absence of a curing agent and the presence or absence of an organic acid metal salt with respect to the flexible curable resin. FIG.
　図８のように、同じ可撓性を有する硬化性樹脂であっても、まず硬化剤がない場合には硬化が進まない。これは硬化温度を１５０℃に設定しても、２００℃以下に設定しても同じである。（比較例８）
可撓性を有する硬化性樹脂と硬化剤を（１：２）のモル比で混ぜたときには、硬化温度が２００℃のとき２０分ほど経過して始めて硬化の兆候（半硬化）が現れる。（比較例７） As shown in FIG. 8, even if the curable resin has the same flexibility, the curing does not proceed unless there is a curing agent. This is the same whether the curing temperature is set to 150 ° C. or 200 ° C. or lower. (Comparative Example 8)
When a curable resin having flexibility and a curing agent are mixed at a molar ratio of (1: 2), a sign of curing (semi-curing) appears only after about 20 minutes when the curing temperature is 200 ° C. (Comparative Example 7)
　これに対して、可撓性を有する硬化性樹脂と硬化剤を（１：２）のモル比で混ぜ、その混合物に加熱中に生成すると推測されるグルタル酸－Ｓｎ塩を２質量％混合すると、硬化温度が１５０℃下では６分経過すると硬化の兆候（半硬化）が見られ、１２分経過すると完全に硬化した。しかも硬化温度が２００℃に設定したときには僅か３分でバインダーが完全に硬化した。（実施例３） On the other hand, when a curable resin having flexibility and a curing agent are mixed at a molar ratio of (1: 2), 2% by mass of glutaric acid-Sn salt presumed to be generated during heating is mixed with the mixture. When the curing temperature was 150 ° C., 6 minutes passed, signs of curing (semi-cured) were observed, and when 12 minutes passed, the film was completely cured. Moreover, when the curing temperature was set to 200 ° C., the binder was completely cured in only 3 minutes. (Example 3)
　このように可撓性を有する硬化性樹脂と硬化剤を（１：２）のモル比で混ぜたものに、グルタル酸－Ｓｎ塩を添加することによって、換言すればグルタル酸－Ｓｎ塩（有機酸金属塩）が樹脂硬化中に生成されることによって、樹脂の硬化が促進され、短い時間（３分程度）で硬化温度が比較的低い設定温度（２００℃程度）でも完全に硬化させることができる。これによって低温接合が可能になる。 By adding glutaric acid-Sn salt to such a mixture of flexible curable resin and curing agent in a molar ratio of (1: 2), in other words, glutaric acid-Sn salt (organic The acid metal salt) is generated during the resin curing, so that the curing of the resin is promoted and can be completely cured even at a relatively low setting temperature (about 200 ° C.) in a short time (about 3 minutes). it can. This enables low temperature bonding.
　硬化促進剤は、硬化性樹脂の硬化促進の他に、上述したように導通性の改善にも寄与する。
図９は、硬化性樹脂の硬化時間とグルタル酸の添加量による表面電気抵抗値の推移を示す特性図である。 The curing accelerator contributes to the improvement of conductivity as described above in addition to the acceleration of curing of the curable resin.
FIG. 9 is a characteristic diagram showing the transition of the surface electrical resistance value depending on the curing time of the curable resin and the addition amount of glutaric acid.
この図より明らかなように、硬化時間が長くなるにつれ表面電気抵抗値が漸減すると共に、グルタル酸の含有量が２質量％よりも４質量％の方が表面電気抵抗値が低くなる傾向にある。したがってグルタル酸の濃度は２～４質量％程度が好適である。 As is clear from this figure, the surface electrical resistance value gradually decreases as the curing time becomes longer, and the surface electrical resistance value tends to be lower when the content of glutaric acid is 4% by mass than 2% by mass. . Accordingly, the concentration of glutaric acid is preferably about 2 to 4% by mass.
　図５～図９の説明で使用した質量％は、図４のようにバインダーの総量を１００重量％としたときのそれぞれの成分量を表している。
バインダーは、硬化性樹脂、硬化剤、硬化促進剤および炭素同素体であるＣＮＴで構成される。
（４）ＣＮＴの分散について
　この発明では硬化性樹脂にＣＮＴを剪断して分散させたものが使用される。
ＣＮＴはチキソ剤（揺変剤）として機能する。 The mass% used in the description of FIGS. 5 to 9 represents the amount of each component when the total amount of the binder is 100% by weight as shown in FIG.
A binder is comprised with CNT which is curable resin, a hardening | curing agent, a hardening accelerator, and a carbon allotrope.
(4) Dispersion of CNT In the present invention, a curable resin obtained by shearing and dispersing CNT is used.
CNT functions as a thixotropic agent (thixotropic agent).
ＣＮＴが凝集を起こすことなく硬化性樹脂中に分散させる技術は、特開２００５－１５４６３０号公報や、特開２００５－８９７３８号公報などに開示されているので、この発明においてもこれら開示技術などを参考にして分散媒が作成される。 Techniques for dispersing CNTs in a curable resin without causing aggregation are disclosed in Japanese Patent Application Laid-Open No. 2005-154630, Japanese Patent Application Laid-Open No. 2005-89738, and the like. A dispersion medium is created with reference.
　バインダー中にＣＮＴが含まれているか否かによってバインダーの粘度特性に影響を与える。
図１０はこの粘度特性を示すもので、曲線ＳａはバインダーにＣＮＴを含有させたものと錫粉末を練り合わせたペースト状はんだの粘度特性であり、曲線ＳｂはＣＮＴを含まないときのバインダーの粘度特性であり、そして曲線ＳｃがＣＮＴを含有させたバインダーの粘度特性である。 The viscosity characteristics of the binder are influenced by whether or not CNT is contained in the binder.
FIG. 10 shows this viscosity characteristic. Curve Sa is the viscosity characteristic of paste solder in which tin powder is mixed with a binder containing CNT, and curve Sb is the viscosity characteristic of the binder when CNT is not included. And the curve Sc is the viscosity characteristic of the binder containing CNTs.
　粘度測定は回転式のものを使用した場合であって、曲線Ｓｃからも明らかなように、１０ｒｐｍ粘度で３０Ｐａ・ｓ（パスカル・秒）、３０ｒｐｍ粘度で約２０Ｐａ・ｓが得られる。
そのときのチキソ比は図１１に示すように１０ｒｐｍ粘度で０．８８程度の値が得られ、ＣＮＴを含まないバインダーでの結果と比較すると、ＣＮＴはバインダーの粘度とチキソ比を同時に引き上げる効能を持つことが分かる。 Viscosity is measured when a rotary type is used. As is apparent from the curve Sc, 30 Pa · s (Pascal · second) is obtained at 10 rpm viscosity, and about 20 Pa · s is obtained at 30 rpm viscosity.
As shown in FIG. 11, the thixo ratio at that time has a value of about 0.88 at a viscosity of 10 rpm. Compared with the result with a binder not containing CNT, CNT has the effect of simultaneously increasing the viscosity of the binder and the thixo ratio. I understand that I have it.
　曲線Ｓａからも明らかなように、ＣＮＴを含有したペースト状はんだは粘度１７０Ｐａ・ｓ、チキソ比０．６５が得られ、スクリーン印刷において良好な粘度は１０ｒｐｍ粘度で１５０Ｐａ・ｓ、チキソ比は０．５～０．７と言われているので、ＣＮＴは、ペースト状はんだに匹敵する粘性特性を与える効能がある。 As is apparent from the curve Sa, the paste-like solder containing CNT has a viscosity of 170 Pa · s and a thixo ratio of 0.65. In screen printing, a good viscosity is 150 Pa · s at 10 rpm viscosity and the thixo ratio is 0.1. Since it is said to be 5 to 0.7, CNT has the effect of giving viscosity characteristics comparable to paste solder.
　ＣＮＴはバインダー内に分散させると加熱溶解しないためＣＮＴを極く少量分散させることによって接合材料の加熱ダレを防止すると共に、印刷供給に必要なチキソ性を改善できる。
このようにＣＮＴを硬化性樹脂であるバインダー中に分散させることによって、良好な粘度特性とチキソ比を実現できることが判明した。 When CNTs are dispersed in a binder, they are not heated and dissolved, so that a very small amount of CNTs can prevent heating of the bonding material and improve the thixotropy required for printing supply.
Thus, it has been found that good viscosity characteristics and a thixo ratio can be realized by dispersing CNTs in a binder which is a curable resin.
　ここで、ＣＮＴは炭素同素体単体又はＣＮＴと炭素同素体の複合物を含むものであって、ナノメートルオーダーのグラファイト系の六員環（一部五員環等が混る場合がある）で構成されたシートをチューブ状に形成した構造を有する物質である。 Here, CNT includes a carbon allotrope or a composite of CNT and carbon allotrope, and is composed of a nanometer-order graphite-based six-membered ring (some of which may be mixed with a five-membered ring, etc.). It is a substance having a structure in which a sheet is formed in a tube shape.
　ＣＮＴは導電性、強度、熱伝導性で驚異的な性能を発揮する、他の物質（例えば金属粒子）と絡めることが出来ると大幅な性能アップを発揮する。一般的にＣＮＴは約０．４～１００nmのサイズ系で長さは数μmの円筒形六員環炭素物質である。 CNTs exhibit tremendous performance in terms of conductivity, strength, and thermal conductivity. If they can be entangled with other substances (for example, metal particles), the performance will be greatly improved. Generally, CNT is a cylindrical six-membered ring carbon material having a size system of about 0.4 to 100 nm and a length of several μm.
　六員環は連続体として構造されている。表面面積が広く強い凝集性を持つ。また、高導電性１０９A／ｃｍ２、高機械的強度はダイヤモンドと同等、高熱伝導率１４００Wm・Ｋという驚異的性能を有している。
ＣＮＴは、硬化性樹脂内での分散性の良さを考慮し、単層ＣＮＴ、２層ＣＮＴ、多層ＣＮＴの中からこの例では多層ＣＮＴを使用した。ＣＮＴは繊維径が５～８０nm、好ましくは８～４０nmのものを使用する。繊維長は、硬化樹脂への分散性を考慮して０．１～３μｍのものを使用する。 Six-membered rings are structured as a continuum. Wide surface area and strong cohesiveness. Further, it has an amazing performance of high conductivity 10 9 A / cm 2 , high mechanical strength equivalent to diamond, and high thermal conductivity 1400 Wm · K.
In consideration of good dispersibility in the curable resin, CNTs were used in this example from single-walled CNTs, double-walled CNTs, and multilayered CNTs. CNTs having a fiber diameter of 5 to 80 nm, preferably 8 to 40 nm are used. A fiber length of 0.1 to 3 μm is used in consideration of dispersibility in a cured resin.
　ＣＮＴの分散量は、図４に示すようにバインダー総量を１００質量％としたとき、０．１～１０質量％、好ましくは３質量％未満で最も好適な分散量は１質量％である。分散量が多いと、凝集性が強くなり、ペースト状とはならなくなる。 As shown in FIG. 4, the dispersion amount of CNT is 0.1 to 10% by mass, preferably less than 3% by mass when the total amount of binder is 100% by mass, and the most preferable dispersion amount is 1% by mass. When the amount of dispersion is large, the cohesiveness becomes strong and the paste is not formed.
　上述した実施例では炭素同素体としてＣＮＴを例示したがカーボンブラックなどの他の炭素同素体とも併用できる。
（５）電子部品のリペアについて
　電子部品接合材料は電子部品搭載基板の製造工程上、電子部品付け替えおよび接合部修理が必ず発生する。その為に一度接合硬化した電子部品接合材料を簡単に取り外せるのが好ましい。 In the embodiment described above, CNT is exemplified as the carbon allotrope, but other carbon allotropes such as carbon black can be used together.
(5) Repair of electronic components Electronic component bonding materials always require electronic component replacement and joint repair in the manufacturing process of the electronic component mounting board. Therefore, it is preferable that the electronic component bonding material once bonded and hardened can be easily removed.
　上述したこの発明にかかる電子部品接合材料を構成する硬化性樹脂は接合温度より高熱環境下（錫の溶融温度以上）で再溶融するので、この発明にかかる電子部品接合材料を使用した場合には、電子部品接合後の修理（リペア）が可能になる。
（６）総合特性について
　既に説明した図４を参照してこの発明に係る電子部品接合材料の総合特性について説明する。
接合材料の組成成分は図４にも示す通りであって、下記のように、
i）導電性粒子（金属フィラー）は、粒径が２５～４５μｍの錫粉末。
ii)　バインダー成分は、主剤としての硬化性樹脂、硬化剤、有機酸そしてＣＮＴからなる。
iii）硬化性樹脂は、可撓性を有するビスフェノール系エポキシ樹脂。
iv）硬化剤としての酸無水物は、コハク酸系酸無水物。
v）エポキシ系樹脂と硬化剤のモル比は、（１：２）。
vi）硬化促進剤としてはグルタル酸に代表される有機酸。
vii）ＣＮＴは、多層ＣＮＴを使用する。
viii) 金属フィラーとして錫を８８質量％とし、バインダーは残部の１２質量％とする配合で電子部品接合材料を作製した。 Since the curable resin constituting the electronic component bonding material according to the present invention described above is remelted in a thermal environment higher than the bonding temperature (above the melting temperature of tin), when the electronic component bonding material according to the present invention is used, , Repair (repair) after joining electronic components becomes possible.
(6) General characteristics of the electronic component bonding material according to the present invention will be described with reference to FIG.
The composition components of the bonding material are as shown in FIG.
i) The conductive particles (metal filler) are tin powder having a particle size of 25 to 45 μm.
ii) The binder component comprises a curable resin as a main agent, a curing agent, an organic acid, and CNT.
iii) The curable resin is a flexible bisphenol-based epoxy resin.
iv) The acid anhydride as the curing agent is a succinic acid anhydride.
v) The molar ratio of the epoxy resin and the curing agent is (1: 2).
vi) Organic acids represented by glutaric acid as curing accelerators.
vii) As the CNT, a multilayer CNT is used.
viii) An electronic component bonding material was prepared by blending tin as a metal filler in an amount of 88% by mass and the binder being the remaining 12% by mass.
　さらに、図４に示したグルタル酸とＣＮＴの質量％は、残部１２質量％を総量１００質量％としたときの値である。これらを調合する製造工程は、以下となる。
（1）硬化性樹脂にＣＮＴを分散させた母剤を作成する。
（2）硬化性樹脂、硬化剤、硬化促進剤を調合した希釈液を作成する。
（3）（1）の母剤と（2）の希釈液を混合し、これに導電性粒子を混ぜ合わせる。
（ａ）比較例５と６について
　比較例５と６は、何れも硬化性樹脂として、可撓性を付与されていない通常の樹脂（標準樹脂）を使用した場合である。
この場合には有機酸やＣＮＴを混錬させたとしても、落下衝撃試験にて１回の衝撃で接合部が破断したため、破断回数の差異は測定できなかった。
（ｂ）比較例1～３について
　比較例１～３は、硬化性樹脂としてこの発明と同じ可撓性を有する硬化性樹脂を使用し、エポキシ樹脂と硬化剤のモル比を（１：１）の当モルに選定した場合である。
比較例２と３は、エポキシ樹脂と硬化剤のモル比が（１：１）となるように選定すると共に、ＣＮＴを増量して３質量％および５質量％それぞれ含有させて実験した。 Furthermore, the mass% of glutaric acid and CNT shown in FIG. 4 is a value when the remaining 12 mass% is 100 mass% in total. The manufacturing process for preparing these is as follows.
(1) Create a base material in which CNTs are dispersed in a curable resin.
(2) Prepare a dilute solution containing a curable resin, a curing agent, and a curing accelerator.
(3) Mix the base material of (1) and the diluted solution of (2), and mix the conductive particles.
(A) About Comparative Examples 5 and 6 Comparative Examples 5 and 6 are cases where an ordinary resin (standard resin) that is not given flexibility is used as the curable resin.
In this case, even if organic acids and CNTs were kneaded, the difference in the number of breaks could not be measured because the joint was broken by a single impact in the drop impact test.
(B) Comparative Examples 1 to 3 Comparative Examples 1 to 3 use a curable resin having the same flexibility as that of the present invention as the curable resin, and the molar ratio of the epoxy resin to the curing agent is (1: 1). This is the case when it is selected as the equivalent mole.
Comparative Examples 2 and 3 were selected such that the molar ratio of the epoxy resin and the curing agent was (1: 1), and the CNTs were increased to contain 3% by mass and 5% by mass, respectively.
　この場合には２００℃３分間での硬化実験の結果、体積抵抗率、粘度およびチキソ比の何れにおいても、体積抵抗率は無限大でかつ粘性が高くなり過ぎて粘度計測不能に陥り論外であった。したがって、ＣＮＴは３質量％未満でなければならない。 In this case, as a result of a curing experiment at 200 ° C. for 3 minutes, the volume resistivity is infinite and the viscosity becomes too high for any of the volume resistivity, viscosity, and thixo ratio, and the viscosity measurement becomes impossible, which is out of the question. It was. Therefore, the CNT must be less than 3% by mass.
　比較例１はＣＮＴを１質量％含有させた場合である。
この場合には２００℃３分間の硬化実験で完全硬化状態となったものの、エポキシ樹脂と硬化剤のモル比が（１：１）であったために体積抵抗率が非常に高い結果となった。
（ｃ）比較例４について
　比較例４は、可撓性を有する硬化性樹脂を使用すると共に、エポキシ系樹脂と硬化剤のモル比が（１：２）となるように選定したものの、グルタル酸とＣＮＴを投入せずに０質量％としたために、体積抵抗率が測定できない程度の高さとなり、しかも２００℃３分間の硬化実験でも未硬化状態であった。
（ｄ）実施例１および２について
　実施例１および２は、可撓性を有する硬化性樹脂を使用すると共に、エポキシ系樹脂と硬化剤のモル比が（１：２）に選定すると共に、ＣＮＴを１質量％それぞれ含有させた場合であり、実施例２はグルタル酸を２質量％、実施例１は４質量％含有されている。 The comparative example 1 is a case where 1 mass% of CNT is contained.
In this case, although it was in a completely cured state in a curing experiment at 200 ° C. for 3 minutes, the molar ratio of the epoxy resin and the curing agent was (1: 1), resulting in a very high volume resistivity.
(C) Comparative Example 4 Comparative Example 4 uses a curable resin having flexibility and is selected so that the molar ratio of the epoxy resin and the curing agent is (1: 2). And 0% by mass without adding CNTs, the volume resistivity was so high that it could not be measured, and it was uncured even in a curing experiment at 200 ° C. for 3 minutes.
(D) Regarding Examples 1 and 2 In Examples 1 and 2, a curable resin having flexibility is used, and the molar ratio of the epoxy-based resin and the curing agent is selected to be (1: 2). In Example 2, 2% by mass of glutaric acid and 4% by mass of Example 1 are contained.
　これら実施例１および２から明らかなように、導電性粒子である錫を８８～９０質量％、残部をバインダーで接合材料を構成すると共に、バインダーのうち、硬化性樹脂に可撓性を有するエポキシ系樹脂とし、硬化剤として酸無水物を使用し、エポキシ系樹脂と硬化剤のモル比1質量％を（１：２）とし、有機酸であるグルタル酸を２～４質量％とし、ＣＮＴを１質量％とするように、グルタル酸やＣＮＴなどの配合を適切な値とすることによって、体積抵抗率を始めとして、落下衝撃特性、２００℃、３分間での硬化特性、加熱によるダレ性、粘度およびチキソ比がそれぞれ所期の値となった。 As is apparent from Examples 1 and 2, the bonding material is composed of 88 to 90% by mass of tin, which is conductive particles, and the remainder is a binder, and among the binder, a curable resin is a flexible epoxy. A resin, an acid anhydride is used as a curing agent, the molar ratio of the epoxy resin and the curing agent is 1% by mass, the organic acid glutaric acid is 2 to 4% by mass, By adjusting the composition of glutaric acid, CNT, etc. to an appropriate value so as to be 1% by mass, starting from volume resistivity, drop impact characteristics, curing characteristics at 200 ° C. for 3 minutes, sagging by heating, Viscosity and thixo ratio were the expected values.
　以上を総合的に判断すると、導電性粒子として錫を使用することで高導電性と低温硬化が可能となり、可撓性を有する硬化性樹脂を使用することによって柔軟性と靱性を付与できるため落下衝撃特性が大幅に改善され、エポキシ系樹脂と硬化剤のモル比を（１：２）に選定しグルタル酸を付加することによって、錫との共存も加わり、硬化時間の短縮と硬化速度の迅速化が達成されるので、これによって低温硬化特性が付与され、またエポキシ系樹脂と硬化剤のモル比を（１：２）に選定すると共に有機酸を混合することによって、体積抵抗率が低下して導電性が大幅に改善され、ＣＮＴを適宜量混合・混練することによって、ダレ性が防止されると共に、適度な粘度特性およびチキソ性が付与された、電子部品接合材料を実現できる。
したがって従来のペースト状はんだに代わる廉価な接合材料を提供できる。 When the above is judged comprehensively, the use of tin as the conductive particles enables high conductivity and low temperature curing, and the use of a flexible curable resin can provide flexibility and toughness. Impact characteristics are greatly improved, and the molar ratio of epoxy resin to curing agent is selected as (1: 2) and glutaric acid is added to add coexistence with tin, shortening the curing time and rapid curing speed. As a result, low temperature curing characteristics are imparted, and by selecting the molar ratio of the epoxy resin and the curing agent to (1: 2) and mixing the organic acid, the volume resistivity decreases. In addition, by appropriately mixing and kneading CNTs in an appropriate amount, it is possible to realize an electronic component bonding material that is prevented from sagging and is imparted with appropriate viscosity characteristics and thixotropy.
Therefore, it is possible to provide an inexpensive bonding material that replaces the conventional paste solder.
　この発明は各種電子部品などを回路基板に実装するときに使用される接合材料として利用できる他、回路基板構成要素や電磁波遮蔽用材料、太陽光発電用回路形成材料にも使用できる。 The present invention can be used as a bonding material used when mounting various electronic components and the like on a circuit board, and can also be used as a circuit board component, an electromagnetic shielding material, and a circuit forming material for photovoltaic power generation.
Ｓａ・・・ＣＮＴを含んだバインダーを用いて錫粉末と練り合わせたペースト状はんだの曲線
Ｓｂ・・・ＣＮＴを含まないバインダーの曲線
Ｓｃ・・・ＣＮＴを含んだバインダーの曲線 Sa ... Paste solder curve kneaded with tin powder using binder containing CNT Sb ... Binder curve not containing CNT Sc ... Binder curve containing CNT

Claims (8)

  1. ＣＮＴを分散させた硬化性樹脂に硬化剤と硬化促進剤を加えたバインダーと導電性粒子からなり、この導電性粒子を上記バインダーに混合・混練させてペースト状となした
    ことを特徴とする電子部品接合材料。     An electron comprising a binder in which a curing agent and a curing accelerator are added to a curable resin in which CNTs are dispersed and conductive particles, and the conductive particles are mixed and kneaded with the binder to form a paste. Component bonding material.
  2. 上記導電性粒子として錫、銀、銅、金、インジウム、ニッケル、パラジウム単体および金属粒子群から選択された２種以上の物質、混合物または合金で構成された粒子が使用されると共に、上記の硬化性樹脂として可撓性を有する硬化性樹脂が使用された
    ことを特徴とする請求項１記載の電子部品接合材料。     As the conductive particles, particles composed of two or more substances, mixtures or alloys selected from tin, silver, copper, gold, indium, nickel, palladium simple substance and metal particle group are used, and the above curing is performed. 2. The electronic component bonding material according to claim 1, wherein a curable resin having flexibility is used as the conductive resin.
  3. 硬化剤に硬化促進剤を併用することで上記硬化性樹脂の硬化促進作用を付与した
    ことを特徴とする請求項１または２記載の電子部品接合材料。     The electronic component bonding material according to claim 1 or 2, wherein the curing accelerator is imparted with a curing acceleration effect by using a curing accelerator in combination with the curing agent.
  4. 硬化剤と硬化促進剤および金属粒子の共存下で生成された物質により短時間硬化作用を付与したこと
    を特徴とする請求項１から請求項３記載の電子部品接合材料。     4. The electronic component bonding material according to claim 1, wherein a curing action is imparted for a short time by a substance generated in the coexistence of a curing agent, a curing accelerator and metal particles.
  5. 上記導電性粒子７０～９５質量％に対し、残部が上記バインダーである
    ことを特徴とする請求項１記載の電子部品接合材料。     The electronic component bonding material according to claim 1, wherein the remaining part is the binder with respect to 70 to 95% by mass of the conductive particles.
  6. 上記バインダーの総量を１００質量％としたとき、上記バインダーを構成する硬化性樹脂が５～５０質量％、好ましくは３０～４０質量％使用され、この硬化性樹脂に分散される上記ＣＮＴは、硬化性樹脂と上記硬化剤および上記硬化促進剤を含めた総量１００質量％に対して０．１～１０質量％、好ましくは３質量％未満で使用され、
    　上記硬化剤が上記硬化性樹脂に対して当モル以上の割合で配合され、上記硬化促進剤が、２～４質量％使用された
    ことを特徴とする請求項１記載の電子部品接合材料。     When the total amount of the binder is 100% by mass, the curable resin constituting the binder is used in an amount of 5 to 50% by mass, preferably 30 to 40% by mass, and the CNT dispersed in the curable resin is cured. 0.1 to 10% by weight, preferably less than 3% by weight, based on a total amount of 100% by weight including the functional resin, the curing agent and the curing accelerator,
    The electronic component bonding material according to claim 1, wherein the curing agent is blended in an amount of an equimolar amount or more with respect to the curable resin, and the curing accelerator is used in an amount of 2 to 4% by mass.
  7. 上記硬化性樹脂は、電子部品接合上必要とする可撓性を有する
    ことを特徴とする請求項１記載の電子部品接合材料。     The electronic component bonding material according to claim 1, wherein the curable resin has flexibility required for electronic component bonding.
  8. 上記電子部品接合材料は、接合温度より高温環境下で硬化性樹脂が再溶融する
    ことを特徴とする請求項１記載の電子部品接合材料。     2. The electronic component bonding material according to claim 1, wherein the electronic component bonding material is such that the curable resin is re-melted in an environment higher than the bonding temperature. 3.
PCT/JP2013/071227 2013-08-06 2013-08-06 Electronic component joint material WO2015019414A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2013/071227 WO2015019414A1 (en) 2013-08-06 2013-08-06 Electronic component joint material
TW103125958A TW201522567A (en) 2013-08-06 2014-07-30 Electronic component joint material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/071227 WO2015019414A1 (en) 2013-08-06 2013-08-06 Electronic component joint material

Publications (1)

Publication Number Publication Date
WO2015019414A1 true WO2015019414A1 (en) 2015-02-12

Family

ID=52460787

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/071227 WO2015019414A1 (en) 2013-08-06 2013-08-06 Electronic component joint material

Country Status (2)

Country Link
TW (1) TW201522567A (en)
WO (1) WO2015019414A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019137797A (en) * 2018-02-13 2019-08-22 大研化学工業株式会社 Thermosetting conductive adhesive and manufacturing method therefor

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5575956A (en) * 1995-07-19 1996-11-19 Hughes Aircraft Company Room-temperature stable, one-component, electrically-conductive, flexible epoxy adhesives
JPH09104855A (en) * 1995-06-07 1997-04-22 Natl Starch & Chem Investment Holding Corp Rapid-curing epoxy adhesive
JP2006120665A (en) * 2004-10-19 2006-05-11 Sumitomo Metal Mining Co Ltd Conductive resin paste composition containing silver and carbon nano tube, and semiconductor device using the same
JP2007149522A (en) * 2005-11-29 2007-06-14 Sumitomo Metal Mining Co Ltd Conductive resin paste composition containing silver and carbon nanotube, and semiconductor device using this
JP2008293821A (en) * 2007-05-25 2008-12-04 Panasonic Corp Conductive paste, circuit board using the same, and electronic/electric device
JP2009117340A (en) * 2007-11-07 2009-05-28 Samsung Electro-Mechanics Co Ltd Conductive paste and printed circuit board using the same
JP2012079682A (en) * 2010-09-09 2012-04-19 Nec Corp Conductive paste and circuit board using the same
JP2012092201A (en) * 2010-10-26 2012-05-17 Kyocera Chemical Corp Electroconductive resin composition, and semiconductor device using the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09104855A (en) * 1995-06-07 1997-04-22 Natl Starch & Chem Investment Holding Corp Rapid-curing epoxy adhesive
US5575956A (en) * 1995-07-19 1996-11-19 Hughes Aircraft Company Room-temperature stable, one-component, electrically-conductive, flexible epoxy adhesives
JP2006120665A (en) * 2004-10-19 2006-05-11 Sumitomo Metal Mining Co Ltd Conductive resin paste composition containing silver and carbon nano tube, and semiconductor device using the same
JP2007149522A (en) * 2005-11-29 2007-06-14 Sumitomo Metal Mining Co Ltd Conductive resin paste composition containing silver and carbon nanotube, and semiconductor device using this
JP2008293821A (en) * 2007-05-25 2008-12-04 Panasonic Corp Conductive paste, circuit board using the same, and electronic/electric device
JP2009117340A (en) * 2007-11-07 2009-05-28 Samsung Electro-Mechanics Co Ltd Conductive paste and printed circuit board using the same
JP2012079682A (en) * 2010-09-09 2012-04-19 Nec Corp Conductive paste and circuit board using the same
JP2012092201A (en) * 2010-10-26 2012-05-17 Kyocera Chemical Corp Electroconductive resin composition, and semiconductor device using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019137797A (en) * 2018-02-13 2019-08-22 大研化学工業株式会社 Thermosetting conductive adhesive and manufacturing method therefor
JP7148949B2 (en) 2018-02-13 2022-10-06 大研化学工業株式会社 Thermosetting conductive adhesive and its manufacturing method

Also Published As

Publication number Publication date
TW201522567A (en) 2015-06-16

Similar Documents

Publication Publication Date Title
CN101437900B (en) Thermosetting resin composition, method for producing the same and circuit board
CN106459718B (en) Thermally and electrically conductive adhesive composition
WO2013125517A1 (en) Conductive particles, method for producing conductive particles, conductive material and connection structure
JPWO2006080247A1 (en) Conductive paste
CN105452414B (en) Electrically conductive adhesive agent, joined body, and joint
KR101293914B1 (en) Conductive ink and device using the same
TWI417399B (en) Composite lead-free solder alloy composition having nano-particles
KR20110049466A (en) Conductive paste and the manufacturing method thereof and the electric device comprising thereof
JP2008293821A (en) Conductive paste, circuit board using the same, and electronic/electric device
JP6203783B2 (en) Conductive adhesive and method for manufacturing electronic substrate
Kwon et al. Dispersion, hybrid interconnection and heat dissipation properties of functionalized carbon nanotubes in epoxy composites for electrically conductive adhesives (ECAs)
TWI360452B (en) Composite lead-free solder composition having nano
JP2007051272A (en) Heat-resistant conductive adhesive
JP2013149466A (en) Anisotropic conductive material, connection structure and method for producing connection structure
JP4703581B2 (en) Conductive filler and solder paste
JP5946978B1 (en) Conductive particle, method for producing conductive particle, conductive material, and connection structure
Li et al. Electrical and mechanical characterization of carbon nanotube filled conductive adhesive
CN109887639A (en) A kind of solderable low temperature curing type function silver paste and preparation method thereof
JP2010285580A (en) Thermosetting resin composition and circuit board
JP6428716B2 (en) Conductive adhesives, joints and joints
WO2015019414A1 (en) Electronic component joint material
Li et al. Nano-conductive adhesives for nano-electronics interconnection
JP5965666B2 (en) Method for manufacturing connection structure and anisotropic conductive material
Hwang et al. Pressureless Cu–Cu bonding using hybrid Cu–epoxy paste and its reliability
Yim et al. Effect of dispersion condition of multi-walled carbon nanotube (MWNT) on bonding properties of solderable isotropic conductive adhesives (ICAs)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13890906

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 13890906

Country of ref document: EP

Kind code of ref document: A1