WO2019050012A1 - Film adhésif pour connexion de circuits et procédé de fabrication associé, procédé de fabrication d'une structure de connexion de circuits et ensemble contenant pour film adhésif - Google Patents

Film adhésif pour connexion de circuits et procédé de fabrication associé, procédé de fabrication d'une structure de connexion de circuits et ensemble contenant pour film adhésif Download PDF

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Publication number
WO2019050012A1
WO2019050012A1 PCT/JP2018/033290 JP2018033290W WO2019050012A1 WO 2019050012 A1 WO2019050012 A1 WO 2019050012A1 JP 2018033290 W JP2018033290 W JP 2018033290W WO 2019050012 A1 WO2019050012 A1 WO 2019050012A1
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WO
WIPO (PCT)
Prior art keywords
adhesive layer
adhesive film
curable composition
circuit connection
circuit
Prior art date
Application number
PCT/JP2018/033290
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English (en)
Japanese (ja)
Inventor
智樹 森尻
友美子 大當
直 工藤
Original Assignee
日立化成株式会社
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 日立化成株式会社 filed Critical 日立化成株式会社
Priority to KR1020207006845A priority Critical patent/KR102569980B1/ko
Priority to JP2019541034A priority patent/JP7210846B2/ja
Priority to KR1020237028180A priority patent/KR20230126743A/ko
Priority to CN201880058646.1A priority patent/CN111094487A/zh
Publication of WO2019050012A1 publication Critical patent/WO2019050012A1/fr

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    • 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
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump 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
    • H01L2224/16221—Disposition the bump 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
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body

Definitions

  • the present invention relates to an adhesive film for circuit connection and a method for manufacturing the same, a method for manufacturing a circuit connection structure, and an adhesive film storage set.
  • circuit connections For example, conductive particles in an adhesive as an adhesive material for connection between a liquid crystal display and a tape carrier package (TCP), connection between a flexible printed wiring board (FPC) and a TCP, or connection between an FPC and a printed wiring board
  • TCP tape carrier package
  • FPC flexible printed wiring board
  • An adhesive film for circuit connection having anisotropic conductivity dispersed therein is used.
  • the circuit members are adhered to each other by the circuit connection portion formed by the adhesive film for circuit connection, and the electrodes on the circuit member are electrically connected via the conductive particles in the circuit connection portion.
  • a circuit connection structure can be obtained.
  • Patent Document 1 a method is proposed in which the conductive particles are unevenly distributed on one side of the anisotropic conductive adhesive sheet, and the conductive particles are separated from each other.
  • the present invention can improve the capture ratio of the conductive particles between the facing electrodes of the circuit connection structure, and the separation between the circuit member and the circuit connection portion does not easily occur in a high temperature and high humidity environment.
  • An adhesive film for circuit connection capable of obtaining a circuit connection structure and a method for producing the same, a method for producing a circuit connection structure using the adhesive film, and an adhesive film housing set provided with the adhesive film The purpose is to
  • the adhesive film for circuit connection comprises a first adhesive layer containing conductive particles, and a second adhesive layer laminated on the first adhesive layer.
  • the ratio of the DSC calorific value of the first adhesive layer to the DSC calorific value of the second adhesive layer is 0.4 or less.
  • the adhesive film for circuit connection it is possible to improve the capture ratio of the conductive particles between the facing electrodes of the circuit connection structure. Therefore, according to this adhesive film for circuit connection, the connection resistance of the opposing electrode of the circuit connection structure can be reduced.
  • the adhesive film for circuit connection it is possible to obtain a circuit connection structure in which peeling between the circuit member and the circuit connection portion is less likely to occur in a high temperature and high humidity environment (for example, 85 ° C., 85% RH). Can.
  • a high temperature and high humidity environment for example, 85 ° C., 85% RH.
  • connection reliability of the circuit connection structure can be improved.
  • the method includes a preparation step of preparing a first adhesive layer, and a second curable composition comprising a second curable composition on the first adhesive layer.
  • a laminating step of laminating the adhesive layer, and the preparing step includes irradiating the first layer of the first curable composition containing conductive particles with light or heating the layer. And curing the material to obtain a first adhesive layer, wherein the ratio of the DSC calorific value of the first adhesive layer to the DSC calorific value of the second adhesive layer is 0.4
  • the first curable composition is cured to be as follows.
  • an adhesive film for circuit connection can be obtained from which a connection structure can be obtained.
  • the first adhesive layer may be a cured product of the first curable composition, and the first curable composition may contain a radically polymerizable compound having a radically polymerizable group.
  • the second adhesive layer may be composed of a second curable composition, and the second curable composition may contain a radically polymerizable compound having a radically polymerizable group.
  • the thickness of the first adhesive layer may be 0.2 to 0.8 times the average particle size of the conductive particles.
  • the above-described adhesive for circuit connection is provided between a first circuit member having a first electrode and a second circuit member having a second electrode. And thermally bonding the first circuit member and the second circuit member with the agent film interposed therebetween to electrically connect the first electrode and the second electrode to each other.
  • this method it is possible to obtain a circuit connection structure which is excellent in the capture ratio of conductive particles between opposing electrodes of the circuit connection structure and in which peeling between the circuit member and the circuit connection portion is less likely to occur in a high temperature and high humidity environment. You can get it.
  • the adhesive film housing set according to one aspect of the present invention includes the above-described adhesive film for circuit connection and a housing member for housing the adhesive film, and the housing member allows the inside of the housing member to be visible from the outside. And the transmittance of light with a wavelength of 365 nm in the viewing portion is 10% or less.
  • the environment using the adhesive film for circuit connection is a room called a clean room, in which the temperature, humidity and cleanliness of the room are managed at a certain level.
  • the adhesive film for circuit connection is shipped from the production site, the adhesive film for circuit connection is housed in a storage member such as a packaging bag so that it is directly exposed to the outside air and does not cause deterioration in quality due to dust and moisture.
  • the container member is made of a transparent material so that various information such as the product name, lot number, expiration date and the like attached to the adhesive film inside can be confirmed from the outside of the container member.
  • a department is provided.
  • the adhesive film for circuit connection described above is stored in a conventional housing member and used after being stored or transported, peeling between the circuit member and the circuit connection is likely to occur in a high temperature and high humidity environment.
  • the inventors of the present invention have made it clear that defects such as a decrease in the connection resistance reduction effect of the adhesive film may occur due to the decrease in the improvement effect of the capture rate and the decrease in the fluidity.
  • the present inventors conducted further studies based on such examination results, the first adhesive layer was made of a cured product of the photocurable composition, and the second adhesive layer was composed of the photocurable composition.
  • the second adhesive layer cures during storage and transport of the adhesive film when the adhesive film is made of a curable composition containing a polymerizable compound capable of reacting with the photopolymerization initiator in the object, causing the above-mentioned failure It was revealed. Therefore, the present inventors are further based on the assumption that the polymerization of the polymerizable compound in the second adhesive layer proceeds by the radical derived from the photopolymerization initiator remaining in the first adhesive layer. As a result of examining, by setting it as an adhesive film accommodation set provided with the above-mentioned specific accommodation member, hardening of the 2nd adhesive layer at the time of storage or transportation can be controlled, and generating of the above-mentioned fault is controlled. I found out what I could do.
  • the adhesive film housing set of one aspect of the present invention in the case of using a compound capable of reacting with the photopolymerization initiator in the first adhesive layer as the polymerizable compound in the second adhesive layer.
  • the capture of the second adhesive layer during storage or transportation of the adhesive film can be suppressed, and peeling between the circuit member and the circuit connection is likely to occur in a high temperature and high humidity environment.
  • By the decrease in the improvement effect of the rate and the decrease in the flowability it is possible to suppress the occurrence of a defect such as the reduction effect of the connection resistance of the adhesive film.
  • the capture ratio of conductive particles between opposing electrodes of the circuit connection structure can be improved, and separation between the circuit member and the circuit connection portion is less likely to occur in a high temperature and high humidity environment.
  • An adhesive film for circuit connection capable of obtaining a circuit connection structure and a method for producing the same, a method for producing a circuit connection structure using the adhesive film, and an adhesive film housing set provided with the adhesive film can do.
  • FIG. 1 is a schematic cross-sectional view showing an adhesive film for circuit connection according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a circuit connection structure according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross section which shows the manufacturing process of the circuit connection structure of one Embodiment of this invention.
  • FIG. 4 is a perspective view showing an adhesive film storage set according to an embodiment of the present invention.
  • (meth) acrylate means at least one of acrylate and a methacrylate corresponding thereto. The same applies to other similar expressions such as "(meth) acryloyl".
  • FIG. 1 is a schematic cross-sectional view showing an adhesive film for circuit connection of one embodiment.
  • an adhesive film 1 for circuit connection (hereinafter, also simply referred to as “adhesive film 1”) is laminated on a first adhesive layer 2 and a first adhesive layer 2. And a second adhesive layer 3.
  • the first adhesive layer 2 contains conductive particles 4.
  • the adhesive film 1 is an anisotropic conductive adhesive film having anisotropic conductivity.
  • the adhesive film 1 is interposed between a first circuit member having a first electrode and a second circuit member having a second electrode, and the first circuit member and the second circuit member are provided.
  • the thermocompression bonding is used to electrically connect the first electrode and the second electrode to each other.
  • the ratio (Cx / Cy) of the DSC calorific value Cx of the first adhesive layer to the DSC calorific value Cy of the second adhesive layer 3 is 0.4 or less.
  • DSC calorific value means a calorific value (J / g) measured by DSC (differential scanning calorimetry, differential scanning calorimetry), and a large DSC calorific value of the adhesive layer means a circuit It means that the calorific value of the adhesive layer at the time of connection of members is large.
  • the DSC calorific value tends to increase as the residual amount of the component (for example, an uncured component such as a polymerizable compound) which reacts by the exothermic reaction in the adhesive layer increases.
  • the DSC calorific value Cx and the DSC calorific value Cy can be determined by performing DSC measurement of the first adhesive layer 2 and the second adhesive layer 3 by the method described in the examples.
  • the adhesive film 1 since the ratio (Cx / Cy) of the DSC calorific value is 0.4 or less, the capture ratio of the conductive particles between the facing electrodes of the circuit connection structure can be improved. Therefore, according to the adhesive film 1, the connection resistance of the opposing electrode of the circuit connection structure can be reduced.
  • the adhesive film 1 since the ratio (Cx / Cy) of DSC calorific value is 0.4 or less, the circuit member and the circuit connection portion in a high temperature and high humidity environment (for example, 85 ° C., 85% RH) Thus, it is possible to obtain a circuit connection structure in which peeling between the two is difficult to occur.
  • the adhesive film 1 since the ratio (Cx / Cy) of the DSC calorific value is 0.4 or less, low connection resistance is maintained even in a high temperature and high humidity environment (for example, 85 ° C., 85% RH) can do. That is, according to the adhesive film 1, the connection reliability of the circuit connection structure can be improved.
  • the adhesive film 1 is also stored and used as an adhesive reel by slitting into a narrow width in the state of the adhesive film with a substrate formed on one surface of the substrate and then winding it around a core. May be
  • This adhesive reel is required to have good blocking resistance such that the adhesive film 1 is not easily peeled off from the substrate when the substrate-attached adhesive film is fed out from the adhesive reel.
  • it may be difficult to obtain good blocking resistance when slitting to a narrow width of about 0.4 to 1.0 mm.
  • the adhesive film 1 of the present embodiment since the ratio (Cx / Cy) of the DSC calorific value is 0.4 or less, sticking (blocking) between the first adhesive layer 2 and the substrate is suppressed. Ru. Therefore, by providing a substrate on the surface opposite to the first adhesive layer 2 of the second adhesive layer 3, good blocking resistance can be achieved even in the case of slitting in a narrow width as described above. Tends to be obtained.
  • the blocking resistance can be evaluated, for example, by a test for confirming whether or not the adhesive reel can be pulled out without any problem after being left in an environment of 30 ° C. for 24 hours.
  • the ratio (Cx / Cy) of the calorific value of DSC can further improve the capture rate of conductive particles, and the circuit member and the circuit connection portion in a high temperature and high humidity environment (for example, 85 ° C., 85% RH) It is preferably 0.40 or less, more preferably 0.30 or less, and still more preferably 0.20 or less, from the viewpoint that peeling between them is less likely to occur.
  • the ratio of DSC calorific value (Cx / Cy) is preferably 0.01 or more from the viewpoint of enhancing the affinity between the first adhesive layer and the second adhesive layer and obtaining more excellent connection reliability. , 0.05 or more.
  • the ratio of DSC calorific value (Cx / Cy) may be 0.01 to 0.40, may be 0.01 to 0.30, and is 0.01 to 0.20. It may be 0.05 to 0.40, may be 0.05 to 0.30, and may be 0.05 to 0.20.
  • the first adhesive layer 2 is made of, for example, a cured product of the first curable composition.
  • the first curable composition may be a photocurable composition or may be a thermosetting composition.
  • the first curable composition is, for example, (A) a polymerizable compound (hereinafter, also referred to as “component (A)"), (B) a polymerization initiator (hereinafter, also referred to as “component (B)”). And (C) conductive particles 4 (hereinafter, also referred to as “component (C)”).
  • component (A) a polymerizable compound
  • component (B) a polymerization initiator
  • component (C) conductive particles 4
  • the first curable composition contains a photopolymerization initiator as the component (B), and the first curable composition has a thermosetting composition.
  • a 1st curable composition contains a thermal-polymerization initiator as (B) component.
  • a first adhesive layer 2 polymerizes the component (A), for example, by irradiating light or heating the layer formed of the first curable composition to form a first curable composition. It is obtained by curing the That is, the first adhesive layer 2 may be composed of the conductive particles 4 and the adhesive component 5 obtained by curing the components other than the conductive particles 4 of the first curable composition.
  • the first adhesive layer 2 may be a cured product obtained by completely curing the first curable composition, or may be a cured product obtained by partially curing the first curable composition. Good. That is, when the first curable composition contains the (A) component and the (B) component, the adhesive component 5 may contain unreacted (A) component and (B) component, You do not need to contain it.
  • the component (A) is, for example, a compound which is polymerized by radicals, cations or anions generated by a polymerization initiator (photopolymerization initiator or thermal polymerization initiator) by irradiation with light (for example, ultraviolet light) or heating.
  • the component (A) may be any of a monomer, an oligomer or a polymer.
  • one type of compound may be used alone, or a plurality of types of compounds may be used in combination.
  • Component (A) has at least one polymerizable group.
  • the polymerizable group is, for example, a group containing a polymerizable unsaturated double bond (ethylenically unsaturated bond).
  • the polymerizable group is preferably a radically polymerizable group that reacts with a radical, from the viewpoint that a desired DSC calorific value is easily obtained, and the reduction effect of connection resistance is further improved, and from the viewpoint of being more excellent in connection reliability. That is, it is preferable that (A) component is a radically polymerizable compound.
  • a radically polymerizable group a vinyl group, an allyl group, a styryl group, an alkenyl group, an alkenylene group, a (meth) acryloyl group, a maleimide group etc. are mentioned, for example.
  • the number of polymerizable groups contained in the component (A) may be 2 or more from the viewpoint that physical properties and crosslink density necessary for reducing connection resistance can be easily obtained after polymerization, and suppress the cure shrinkage during polymerization From the viewpoint, it may be 10 or less.
  • a polymerizable compound outside the above range may be additionally used.
  • component (A) examples include (meth) acrylate compounds, maleimide compounds, vinyl ether compounds, allyl compounds, styrene derivatives, acrylamide derivatives, nadiimide derivatives, natural rubber, isoprene rubber, butyl rubber, nitrile rubber, butadiene rubber, styrene Butadiene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber and the like can be mentioned.
  • (meth) acrylate compound epoxy (meth) acrylate, (poly) urethane (meth) acrylate, methyl (meth) acrylate, polyether (meth) acrylate, polyester (meth) acrylate, polybutadiene (meth) acrylate, silicone acrylate Ethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl ( Meta) acrylate, 2-hydroxyethyl (meth) acrylate, isopropyl (meth) acrylate, hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, isobornyl (meth) Crylates, isodecyl (meth)
  • maleimide compound 1-methyl-2,4-bismaleimide benzene, N, N'-m-phenylenebismaleimide, N, N'-p-phenylenebismaleimide, N, N'-m-toluylene bismaleimide N, N'-4,4-biphenylene bismaleimide, N, N'-4,4- (3,3'-dimethyl-biphenylene) bismaleimide, N, N'-4,4- (3,3 ' -Dimethyldiphenylmethane) bismaleimide, N, N'-4,4- (3,3'-diethyldiphenylmethane) bismaleimide, N, N'-4,4-diphenylmethane bismaleimide, N, N'-4,4- Diphenylpropane bismaleimide, N, N'-4, 4-diphenylether bismaleimide, N, N'-3, 3-diphenylsulfone bismaleimide, 2, 2-
  • vinyl ether compounds include diethylene glycol divinyl ether, dipropylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and trimethylolpropane trivinyl ether.
  • allyl compound 1,3-diallyl phthalate, 1,2-diallyl phthalate, triallyl isocyanurate and the like can be mentioned.
  • the component (A) is preferably a (meth) acrylate compound from the viewpoint of being excellent in the balance between the curing reaction rate and the physical properties after curing.
  • Component (A) is a (poly) urethane (meth) acrylate compound (urethane) from the viewpoint of achieving both excellent cohesion for reducing connection resistance and elongation for improving adhesion and obtaining more excellent adhesion properties. It may be a (meth) acrylate compound or a polyurethane (meth) acrylate compound).
  • the component (A) may be a (meth) acrylate compound having a high Tg skeleton such as dicyclopentadiene from the viewpoint of improving the cohesion and reducing the connection resistance.
  • the component (A) balances the crosslink density and the cure shrinkage, further reduces the connection resistance, and from the viewpoint of improving connection reliability, the terminal or side of thermoplastic resin such as acrylic resin, phenoxy resin, polyurethane resin, etc. It may be a compound (for example, polyurethane (meth) acrylate) in which a polymerizable group such as a vinyl group, an allyl group or a (meth) acryloyl group is introduced into a chain.
  • the weight average molecular weight of the component (A) may be 3,000 or more, 5,000 or more, or 10,000 or more from the viewpoint of excellent balance between the crosslink density and the cure shrinkage.
  • the weight average molecular weight of the component (A) may be 1,000,000 or less, 500,000 or less, or 250,000 or less, from the viewpoint of excellent compatibility with other components.
  • a weight average molecular weight says the value measured using the calibration curve by standard polystyrene from a gel permeation chromatograph (GPC) according to the conditions as described in an Example.
  • the component (A) preferably contains, as the (meth) acrylate compound, a radically polymerizable compound having a phosphoric acid ester structure represented by the following general formula (1).
  • the adhesive strength of the inorganic substance (metal or the like) to the surface is improved, and for example, it is suitable for bonding the electrodes (for example, the circuit electrodes).
  • n represents an integer of 1 to 3 and R represents a hydrogen atom or a methyl group.
  • the radically polymerizable compound having a phosphoric acid ester structure is obtained, for example, by reacting phosphoric anhydride and 2-hydroxyethyl (meth) acrylate.
  • Specific examples of the radically polymerizable compound having a phosphoric acid ester structure include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate and the like.
  • the content of the component (A) is 5% by mass on the basis of the total mass of the first curable composition from the viewpoint of easily obtaining the crosslinking density necessary to reduce the connection resistance and improve the connection reliability. It may be more than, 10 mass% or more may be sufficient, and 20 mass% or more may be sufficient.
  • the content of the component (A) may be 90% by mass or less and 80% by mass or less based on the total mass of the first curable composition from the viewpoint of suppressing curing shrinkage during polymerization. It may be 70% by mass or less.
  • the component (B) is a radical by irradiation of light including a wavelength within the range of 150 to 750 nm, preferably light including a wavelength within the range of 254 to 405 nm, and more preferably ultraviolet light (eg, ultraviolet light) including a wavelength of 365 nm.
  • ultraviolet light eg, ultraviolet light
  • a photopolymerization initiator (photo radical polymerization initiator, photo cation polymerization initiator or photo anion polymerization initiator) that generates a cation or an anion, and a thermal polymerization initiator (a radical, a cation or an anion is generated by heat ( It may be a thermal radical polymerization initiator, a thermal cationic polymerization initiator or a thermal anionic polymerization initiator).
  • the desired DSC calorific value can be easily obtained, and from the viewpoint that the reduction effect of connection resistance is further improved and the connection reliability is more excellent, and the curing in a short time at a low temperature becomes easier, It is preferable that it is a radical polymerization initiator (photo radical polymerization initiator or thermal radical polymerization initiator).
  • a radical polymerization initiator photo radical polymerization initiator or thermal radical polymerization initiator.
  • the first curable composition may contain both a photopolymerization initiator and a thermal polymerization initiator as the component (B).
  • the photo radical polymerization initiator is decomposed by light to generate free radicals. That is, the photo radical polymerization initiator is a compound which generates a radical by the application of light energy from the outside.
  • a radical photopolymerization initiator oxime ester structure, bisimidazole structure, acridine structure, ⁇ -aminoalkylphenone structure, aminobenzophenone structure, N-phenylglycine structure, acyl phosphine oxide structure, benzyl dimethyl ketal structure, ⁇ -hydroxy
  • the compound which has structures, such as an alkyl phenone structure, is mentioned.
  • the photo radical polymerization initiator is preferably selected from the group consisting of an oxime ester structure, an ⁇ -aminoalkylphenone structure and an acyl phosphine oxide structure from the viewpoint that a desired DSC calorific value is easily obtained and from the viewpoint of being excellent in the reduction effect of connection resistance. It is preferred to have at least one structure selected.
  • the compound having an oxime ester structure examples include 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) ) Oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-o-benzoyloxime, 1,3-diphenylpropanetrione- 2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- ( o-Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-ca Bazoru-3-
  • the compound having an ⁇ -aminoalkylphenone structure examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1 And -morpholinophenyl) -butanone-1 and the like.
  • the compound having an acylphosphine oxide structure include bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl)- Examples thereof include phenyl phosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the thermal radical polymerization initiator is thermally decomposed to generate free radicals. That is, the thermal radical polymerization initiator is a compound which generates a radical by the application of thermal energy from the outside.
  • the heat radical polymerization initiator can be optionally selected from conventionally known organic peroxides and azo compounds.
  • an organic peroxide having a one-minute half-life temperature of 90 to 175 ° C. and a weight average molecular weight of 180 to 1000 is preferably used from the viewpoints of stability, reactivity and compatibility. Be When the one-minute half-life temperature is in this range, the storage stability is further improved, the radical polymerization property is sufficiently high, and curing in a short time becomes possible.
  • organic peroxides include 1,1,3,3-tetramethylbutylperoxy neodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxy Dicarbonate, cumylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate T-Butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) Hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl
  • the azo compound examples include 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), and 2,2'-azobisisobutyro.
  • examples thereof include nitrile, 2,2'-azobis (2-methylbutyronitrile), 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (1-cyclohexanecarbonitrile) and the like.
  • the content of the component (B) is 0.1% by mass or more on the basis of the total mass of the first curable composition, from the viewpoint of excellent fast curing and the viewpoint of reducing the connection resistance. It may be 0.5% by mass or more.
  • the content of the component (B) may be 20% by mass or less on the basis of the total mass of the first curable composition, from the viewpoint of improving the storage stability and from the viewpoint of being excellent in the reduction effect of connection resistance. And 10% by mass or less, and may be 5% by mass or less.
  • the first curable composition preferably contains at least one of a photopolymerization initiator and a thermal polymerization initiator as the component (B) from the viewpoint that a desired viscosity can be easily obtained, and adhesion for circuit connection It is more preferable to contain a photoinitiator from a viewpoint which manufacture of an agent film becomes easy.
  • the component (C) is not particularly limited as long as it is a particle having conductivity, and metal particles composed of metals such as Au, Ag, Ni, Cu, solder, conductive carbon particles composed of conductive carbon, etc. It may be.
  • the component (C) is a coated conductive particle comprising a core containing nonconductive glass, ceramic, plastic (polystyrene etc.) and the like, and a covering layer containing the above metal or conductive carbon and covering the core Good.
  • coated conductive particles comprising a metal particle formed of a heat-melting metal or a core containing a plastic and a coating layer containing a metal or conductive carbon and covering the core are preferably used. In this case, since it is easy to deform the cured product of the first curable composition by heating or pressing, when the electrodes are electrically connected, the contact area between the electrode and the component (C) is The conductivity between the electrodes can be further improved.
  • the component (C) is an insulating coated conductive particle comprising the above-mentioned metal particles, conductive carbon particles, or coated conductive particles, and an insulating material such as a resin, and having an insulating layer coating the surface of the particles. Good. If the component (C) is an insulating coated conductive particle, even if the content of the component (C) is large, the surface of the particle is coated with a resin, so a short circuit due to contact between the components (C) The occurrence can be suppressed, and the insulation between adjacent electrode circuits can also be improved.
  • the component (C) is used singly or in combination of two or more of the various conductive particles described above.
  • the maximum particle size of the component (C) needs to be smaller than the minimum distance between the electrodes (the shortest distance between adjacent electrodes).
  • the maximum particle size of the component (C) may be 1.0 ⁇ m or more, 2.0 ⁇ m or more, or 2.5 ⁇ m or more from the viewpoint of excellent dispersibility and conductivity.
  • the maximum particle size of the component (C) may be 50 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity.
  • the particle diameter of 300 arbitrary conductive particles (pcs) is measured by observation using a scanning electron microscope (SEM), and the largest value obtained is the maximum particle diameter of the component (C). I assume.
  • the particle diameter of the component (C) is the diameter of a circle circumscribing the conductive particles in the image of the SEM.
  • the average particle diameter of the component (C) may be 1.0 ⁇ m or more, 2.0 ⁇ m or more, or 2.5 ⁇ m or more from the viewpoint of excellent dispersibility and conductivity.
  • the average particle size of the component (C) may be 50 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity.
  • the particle diameter of 300 arbitrary conductive particles (pcs) is measured by observation using a scanning electron microscope (SEM), and the average value of the obtained particle diameters is defined as an average particle diameter.
  • the component (C) is preferably dispersed uniformly.
  • Particle density of the component (C) first in the adhesive layer 2, from the viewpoint of improving the insulating property between adjacent electrodes may be at 100000pcs / mm 2 or less, may be at 50000pcs / mm 2 or less, It may be 10000 pcs / mm 2 or less.
  • the content of the component (C) may be 0.1% by volume or more, and 1% by volume or more, based on the total volume in the first adhesive layer, from the viewpoint of being able to further improve the conductivity. It may be 5% by volume or more. From the viewpoint of easily suppressing a short circuit, the content of the component (C) may be 50% by volume or less, 30% by volume or less, or 20% by volume, based on the total volume in the first adhesive layer. % Or less.
  • the content of the component (C) in the first curable composition (based on the total volume of the first curable composition) may be the same as the above range.
  • the content of the component (C) may be 0.05% by mass or more based on the total mass of the first adhesive layer from the viewpoint of being able to further improve the conductivity, 0.5% by mass Or more, and may be 2.5% by mass or more.
  • the content of the component (C) may be 25% by mass or less, 15% by mass or less, or 10% by mass, based on the total mass of the first adhesive layer, from the viewpoint of easily suppressing a short circuit. % Or less. If the content of the component (C) is in the above range, the effects of the present invention tend to be remarkably exhibited.
  • content of (C) component on the basis of the total mass of a 1st curable composition may be the same as the said range.
  • the first curable composition may further contain other components other than the (A) component, the (B) component and the (C) component.
  • Other components include, for example, thermoplastic resins, coupling agents and fillers. These components may be contained in the first adhesive layer 2.
  • thermoplastic resin examples include phenoxy resin, polyester resin, polyamide resin, polyurethane resin, polyester urethane resin, acrylic rubber and the like.
  • the first curable composition contains a thermoplastic resin
  • the first adhesive layer can be easily formed.
  • the first curable composition contains a thermoplastic resin
  • the thermoplastic resin has a functional group such as a hydroxyl group, the adhesiveness of the first adhesive layer is likely to be improved.
  • the content of the thermoplastic resin may be, for example, 5% by mass or more and 80% by mass or less based on the total mass of the first curable composition.
  • silane coupling agents having an organic functional group such as (meth) acryloyl group, mercapto group, amino group, imidazole group, epoxy group, silane compounds such as tetraalkoxysilane, tetraalkoxytitanate derivatives, polydialkyl A titanate derivative etc. are mentioned.
  • adhesion can be further improved.
  • the content of the coupling agent may be, for example, 0.1% by mass or more and 20% by mass or less based on the total mass of the first curable composition.
  • the filler includes, for example, a nonconductive filler (eg, nonconductive particles).
  • a nonconductive filler eg, nonconductive particles
  • the filler may be either an inorganic filler or an organic filler.
  • the inorganic filler include metal oxide particles such as silica particles, alumina particles, silica-alumina particles, titania particles, and zirconia particles; and inorganic particles such as nitride particles.
  • the organic filler include organic particles such as silicone particles, methacrylate-butadiene-styrene particles, acryl-silicone particles, polyamide particles and polyimide particles. These microparticles may have a uniform structure or may have a core-shell type structure.
  • the maximum diameter of the filler is preferably less than the minimum particle diameter of the conductive particles 4.
  • the content of the filler may be, for example, 0.1% by volume or more and 50% by volume or less based on the total volume of the first curable composition.
  • the content of the filler may be, for example, 0.05% by mass or more and 25% by mass or less based on the total mass of the first curable composition.
  • the first curable composition may contain other additives such as a softener, an accelerator, an antidegradant, a colorant, a flame retardant, and a thixotropic agent.
  • the content of these additives may be, for example, 0.1 to 10% by mass based on the total mass of the first curable composition. These additives may be contained in the first adhesive layer 2.
  • the first curable composition may contain a thermosetting resin in place of (A) component and (B) component, or in addition to (A) component and (B) component.
  • the thermosetting resin is a resin that is cured by heat and has at least one thermosetting group.
  • the thermosetting resin is, for example, a compound which crosslinks by reacting with the curing agent by heat.
  • One type of compound may be used alone as the thermosetting resin, or a plurality of types of compounds may be used in combination.
  • thermosetting group is, for example, an epoxy group, an oxetane group, an isocyanate group, or the like from the viewpoint that a desired DSC calorific value can be easily obtained and the reduction effect of connection resistance is further improved and the connection reliability is more excellent. You may
  • thermosetting resin examples include bisphenol epoxy resin which is a reaction product of epichlorohydrin and bisphenol A, F, AD etc., epoxy which is a reaction product of epichlorohydrin and phenol novolak, cresol novolac etc.
  • Epoxy resins such as novolac resins, naphthalene epoxy resins having a skeleton containing a naphthalene ring, glycidyl amines, various epoxy compounds having two or more glycidyl groups in one molecule, and the like can be mentioned.
  • the content of the thermosetting resin in the first curable composition is, for example, the total mass of the first curable composition. As a standard, it may be 20 mass% or more, and may be 80 mass% or less.
  • the content of the thermosetting resin in the first curable composition is, for example, the total mass of the first curable composition As a standard, it may be 30 mass% or more, and may be 70 mass% or less.
  • the first curable composition may contain the above-mentioned curing agent of the thermosetting resin.
  • a hardening agent of thermosetting resin a thermal radical generating agent, a thermal cation generating agent, a thermal anion generating agent etc. are mentioned, for example.
  • the content of the curing agent may be, for example, 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the thermosetting resin.
  • the first adhesive layer 2 may contain components derived from the first curable composition such as unreacted components (A) and (B).
  • the unreacted (B) component remains in the first adhesive layer 2 during storage and transportation
  • a part of the second curable composition in the second adhesive layer 3 is cured, and peeling between the circuit member and the circuit connection is likely to occur under a high temperature and high humidity environment. It is inferred that the reduction effect of the improvement effect of the above and the reduction of the fluidity cause a failure such as the reduction effect of the connection resistance of the adhesive film 1.
  • the content of the component (B) in the first adhesive layer 2 may be 15% by mass or less based on the total mass of the first adhesive layer from the viewpoint of suppressing the occurrence of the above-mentioned failure. And 10% by mass or less, and may be 5% by mass or less. Content of (B) component in the 1st adhesive bond layer 2 may be 0.1 mass% or more based on the total mass of a 1st adhesive bond layer.
  • the 1st adhesive bond layer 2 contains a photoinitiator as a (B) component, generation
  • the DSC calorific value of the first curable composition may be 5 J / g or more, and 10 J / g or more from the viewpoint that the cohesion necessary for obtaining good reliability after curing can be easily obtained. It may well be 30 J / g or more.
  • the DSC calorific value of the first curable composition may be 300 J / g or less and may be 200 J / g or less, from the viewpoint of reducing curing shrinkage during curing and obtaining good reliability. It may be less than / g.
  • the DSC calorific value Cx of the first adhesive layer 2 may be 0.1 J / g or more from the viewpoint of improving the adhesion with the second adhesive layer 3 and obtaining good reliability, 1 J / G or more, and may be 2.5 J / g or more.
  • the DSC calorific value Cx further improves the capture rate of the conductive particles, and peeling between the circuit member and the circuit connection in a high temperature and high humidity environment (for example, 85 ° C., 85% RH) is less likely to occur. In view of the above, it may be 100 J / g or less, 50 J / g or less, and 35 J / g or less.
  • the DSC calorific value Cx can be adjusted by changing the composition of the first curable composition, changing the curing conditions of the first curable composition, and the like.
  • the thickness d1 of the first adhesive layer 2 may be 0.2 times or more of the average particle diameter of the conductive particles 4 from the viewpoint of easily suppressing the short circuit due to the aggregation of the conductive particles 4, and 0.3 or more times It may be.
  • the thickness d1 of the first adhesive layer 2 makes it easy for the conductive particles 4 to be trapped between the electrodes, and for the conductive particles to be efficiently flattened at the time of thermocompression bonding, and the connection resistance can be further reduced,
  • the average particle diameter of the conductive particles 4 may be 0.8 times or less and may be 0.7 times or less. From these viewpoints, the thickness d1 of the first adhesive layer 2 may be 0.2 to 0.8 times and 0.3 to 0.7 times the average particle diameter of the conductive particles 4 Good.
  • the conductive particles in the first adhesive layer 2 A part of 4 may project from the first adhesive layer 2 to the second adhesive layer 3 side.
  • the boundary S between the first adhesive layer 2 and the second adhesive layer 3 is located in the space between the adjacent conductive particles 4.
  • the conductive particles 4 may not be exposed on the surface 2 a of the first adhesive layer 2 opposite to the second adhesive layer 3, and the opposite surface 2 a may be flat.
  • the thickness d1 of the first adhesive layer 2 may be appropriately set according to the height of the electrode of the circuit member to be bonded.
  • the thickness d1 of the first adhesive layer 2 may be, for example, 0.5 ⁇ m or more, and may be 20 ⁇ m or less.
  • the length of the exposed portion of the conductive particles 4 may be, for example, 0.1 ⁇ m or more and 20 ⁇ m or less.
  • the second adhesive layer 3 is made of, for example, a second curable composition.
  • the second curable composition contains, for example, (a) a polymerizable compound (hereinafter also referred to as component (a)) and (b) a polymerization initiator (hereinafter also referred to as component (b)).
  • the second curable composition may be a thermosetting composition containing a thermal polymerization initiator as component (b), and is a photocurable composition containing a photopolymerization initiator as component (b). It may be a mixture of a thermosetting composition and a photocurable composition.
  • the second curable composition constituting the second adhesive layer 3 is an uncured curable composition which can flow at the time of circuit connection, and is, for example, an uncured curable composition.
  • the component (a) is, for example, a compound which is polymerized by radicals, cations or anions generated by a polymerization initiator (photopolymerization initiator or thermal polymerization initiator) by irradiation with light (for example, ultraviolet light) or heating.
  • a polymerization initiator photopolymerization initiator or thermal polymerization initiator
  • light for example, ultraviolet light
  • the component (a) the compounds exemplified as the component (A) can be used.
  • the component (a) is reactive by a radical from the viewpoint that the connection in a short time at a low temperature becomes easy and a desired DSC calorific value is easily obtained, and the reduction effect of the connection resistance is further improved and the connection reliability is more excellent.
  • it is a radically polymerizable compound which has a radically polymerizable group.
  • preferred radically polymerizable compounds in the component (a) and combinations of preferred radically polymerizable compounds are the same as the component (A).
  • adhesion is achieved by containing the adhesive film in a housing member described later The curing of the second curable composition tends to be significantly suppressed during storage or transport of the agent film.
  • the component (a) may be a monomer, an oligomer or a polymer.
  • the component (a) may be the same as or different from the component (A).
  • the content of the component (a) is 10% by mass on the basis of the total mass of the second curable composition from the viewpoint of easily obtaining the crosslinking density necessary to reduce the connection resistance and improve the connection reliability. It may be more than, 20 mass% or more may be sufficient, and 30 mass% or more may be sufficient.
  • the content of the component (a) may be 90% by mass or less based on the total mass of the second curable composition from the viewpoint of suppressing curing shrinkage during polymerization and obtaining good reliability, 80 It may be not more than mass% and may be not more than 70 mass%.
  • component (b) component: polymerization initiator As the component (b), the same polymerization initiator as the polymerization initiator exemplified as the component (B) can be used.
  • Component (b) is preferably a radical polymerization initiator. Examples of preferable radical polymerization initiators in the component (b) are the same as the component (B).
  • one type of compound may be used alone, or a plurality of types of compounds may be used in combination.
  • the content of the component (b) is 0.1% by mass or more based on the total mass of the second curable composition from the viewpoint of facilitating connection in a short time at low temperature and from the viewpoint of being excellent in connection reliability. May be 0.5% by mass or more, and 1% by mass or more. From the viewpoint of pot life, the content of the component (b) may be 30% by mass or less, may be 20% by mass or less, and 10% by mass or less based on the total mass of the second curable composition. It may be.
  • the second curable composition may further contain other components other than the (a) component and the (b) component.
  • other components include thermoplastic resins, coupling agents, fillers, softeners, accelerators, deterioration inhibitors, coloring agents, flame retardants, thixotropic agents, and the like.
  • the details of the other components are the same as the details of the other components in the first adhesive layer 2.
  • the second curable composition may contain a thermosetting resin in place of (a) component and (b) component or in addition to (a) component and (b) component.
  • the second curable composition may contain a curing agent used to cure the thermosetting resin.
  • the thermosetting resin and the curing agent the same thermosetting resin and curing agent as the thermosetting resin and the curing agent exemplified as the other components in the first curable composition can be used.
  • the content of the thermosetting resin in the second curable composition is, for example, the total mass of the second curable composition. As a standard, it may be 20 mass% or more, and may be 80 mass% or less.
  • the content of the thermosetting resin in the second curable composition is, for example, the total mass of the second curable composition. As a standard, it may be 20 mass% or more, and may be 80 mass% or less.
  • the content of the curing agent may be the same as the range described as the content of the curing agent in the first curable composition.
  • the content of the conductive particles 4 in the second adhesive layer 3 may be, for example, 1% by mass or less, or 0% by mass, based on the total mass of the second adhesive layer.
  • the second adhesive layer 3 preferably does not contain the conductive particles 4.
  • the DSC calorific value Cy of the second adhesive layer 3 is 10 J / g or more from the viewpoint of easily obtaining the cohesion necessary for obtaining good reliability after curing and easily improving connection reliability. It may be 30 J / g or more and 50 J / g or more.
  • the DSC calorific value Cy may be 300 J / g or less, 200 J / g or less, or 150 J / g or less from the viewpoint of suppressing curing shrinkage during polymerization and obtaining good reliability. .
  • the DSC calorific value Cy can be adjusted, for example, by changing the composition of the second curable composition.
  • the thickness d2 of the second adhesive layer 3 may be appropriately set in accordance with the height of the electrode of the circuit member to be bonded.
  • the thickness d2 of the second adhesive layer 3 may be 5 ⁇ m or more from the viewpoint of being able to fill the space between the electrodes sufficiently to seal the electrodes and to obtain better reliability. It may be 200 ⁇ m or less.
  • Ratio of thickness d1 of first adhesive layer 2 to thickness d2 of second adhesive layer 3 (thickness d1 of first adhesive layer 2 thickness d2 of second adhesive layer 3) May be one or more and 1000 or less from the viewpoint of being able to fill the space between the electrodes sufficiently to seal the electrodes and to obtain better reliability.
  • Thickness of adhesive film 1 (sum of thicknesses of all layers constituting adhesive film 1.
  • thickness d 1 of first adhesive layer 2 and thickness of second adhesive layer 3 ) May be, for example, 5 ⁇ m or more and 200 ⁇ m or less.
  • the adhesive film for circuit connection may be composed of two layers of a first adhesive layer and a second adhesive layer, and other than the first adhesive layer and the second adhesive layer (For example, the third adhesive layer) may be composed of three or more layers.
  • the third adhesive layer may be a layer having a composition similar to that described above for the first adhesive layer or the second adhesive layer, and the first adhesive layer or the second adhesive layer A layer having the same physical properties as the physical properties (for example, the DSC calorific value) described above, and having a thickness similar to the thickness described above for the first adhesive layer or the second adhesive layer, Good.
  • the circuit connection adhesive film may, for example, further comprise a third adhesive layer on the side opposite to the second adhesive layer in the first adhesive layer.
  • the third adhesive layer is made of, for example, the second curable composition (for example, a thermosetting composition) as in the second adhesive layer.
  • the adhesive film for circuit connection of the said embodiment is an anisotropically conductive adhesive film which has anisotropic conductivity
  • the adhesive film for circuit connections has the electroconductivity which does not have anisotropic conductivity. It may be an adhesive film.
  • ⁇ Method of producing adhesive film for circuit connection> for example, a preparation step (first preparation step) of preparing the first adhesive layer 2 described above, and the first adhesive layer 2. And a laminating step of laminating the second adhesive layer 3 described above.
  • the method for producing the circuit connection adhesive film 1 may further include a preparation step (second preparation step) of preparing the second adhesive layer 3.
  • the first adhesive layer 2 is prepared, for example, by forming the first adhesive layer 2 on the substrate to obtain a first adhesive film. Specifically, first, the (A) component, the (B) component and the (C) component, and other components added as needed are added to the organic solvent, and dissolved by stirring, mixing, etc. Alternatively, the varnish composition is prepared by dispersing. Thereafter, the varnish composition is applied onto the substrate subjected to release treatment using a knife coater, roll coater, applicator or the like, and then the organic solvent is volatilized by heating to form a first curable composition on the substrate. A layer consisting of the composition is formed. Subsequently, the layer comprising the first curable composition is irradiated with light or heated to cure the first curable composition and form the first adhesive layer 2 on the substrate. (Curing process). Thereby, a first adhesive film is obtained.
  • organic solvent used for preparation of a varnish composition what has the characteristic which can melt
  • the substrate is not particularly limited as long as it has heat resistance that can withstand the heating conditions at the time of volatilizing the organic solvent when the first curable composition is cured by light, and the first curability can be obtained.
  • the composition is cured by heating, there is no particular limitation as long as it has heat resistance that can withstand the heating conditions for volatilizing the organic solvent and the heating conditions for curing the first curable composition. .
  • stretched polypropylene OPP
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • polyethylene isophthalate polybutylene terephthalate
  • polyolefin polyacetate
  • polycarbonate polyphenylene sulfide
  • polyamide polyimide
  • cellulose ethylene / acetic acid
  • a base material for example, a film
  • a vinyl copolymer made of a vinyl copolymer, polyvinyl chloride, polyvinylidene chloride, a synthetic rubber system, a liquid crystal polymer or the like
  • a base material for example, a film
  • the heating conditions for volatilizing the organic solvent from the varnish composition applied to the substrate are preferably conditions under which the organic solvent is sufficiently volatilized.
  • the heating conditions may be, for example, 40 ° C. or more and 120 ° C. or less for 0.1 minutes or more and 10 minutes or less.
  • irradiation light for example, ultraviolet light
  • Light irradiation can be performed using, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like.
  • the amount of light irradiation may be adjusted so that the ratio of DSC calorific value (Cx / Cy) is 0.4 or less.
  • the irradiation amount of light may be, for example, 100 mJ / cm 2 or more, 200 mJ / cm 2 or more, or 300 mJ / cm 2 or more as an integrated light amount of light with a wavelength of 365 nm.
  • the dose of light for example, an accumulated light quantity of the wavelength 365nm light, may be at 10000 mJ / cm 2 or less, may be at 5000 mJ / cm 2 or less, may be at 3000 mJ / cm 2 or less.
  • the light irradiation amount (integrated light amount of light) is larger, the DSC heat generation amount Cx tends to be smaller, and the ratio (Cx / Cy) of the DSC heat generation amount tends to be smaller.
  • the heating conditions in the curing step may be adjusted so that the ratio of DSC calorific value (Cx / Cy) is 0.4 or less.
  • the heating conditions may be, for example, 30 ° C. to 300 ° C. for 0.1 minutes to 5000 minutes, and 50 ° C. to 150 ° C. for 0.1 minutes to 3000 minutes. As the heating temperature is higher, the DSC calorific value Cx tends to be smaller, and the DSC calorific value ratio (Cx / Cy) tends to be smaller. Further, as the heating time is longer, the DSC calorific value Cx tends to be smaller, and the DSC calorific value ratio (Cx / Cy) tends to be smaller.
  • the second adhesive layer 3 is prepared by forming the second adhesive layer 3 on the substrate to obtain a second adhesive film.
  • the second adhesive layer 3 may be laminated on the first adhesive layer 2 by laminating the first adhesive film and the second adhesive film.
  • the varnish composition obtained by using the (a) component and the (b) component and other components added as needed is applied onto the adhesive layer 2 and the first solvent is removed by volatilizing the organic solvent.
  • the second adhesive layer 3 may be laminated on the adhesive layer 2 of the above.
  • Lamination may be performed, for example, under heating conditions of 0 to 80 ° C.
  • FIG. 2 is a schematic cross section which shows the circuit connection structure of one Embodiment.
  • the circuit connection structure 10 includes a first circuit board 11 and a first circuit member 13 having a first electrode 12 formed on the major surface 11 a of the first circuit board 11.
  • a second circuit member 16 having a second circuit board 14 and a second electrode 15 formed on the main surface 14a of the second circuit board 14, a first circuit member 13 and a second circuit member And a circuit connection portion 17 disposed between the first and second electrodes 12 and 15 for electrically connecting the first electrode 12 and the second electrode 15 to each other.
  • the first circuit member 13 and the second circuit member 16 may be the same as or different from each other.
  • the first circuit member 13 and the second circuit member 16 may be a glass substrate or a plastic substrate on which electrodes are formed, a printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor silicon IC chip or the like.
  • the first circuit board 11 and the second circuit board 14 may be formed of a semiconductor, an inorganic substance such as glass or ceramic, an organic substance such as polyimide or polycarbonate, or a composite such as glass / epoxy.
  • the first electrode 12 and the second electrode 15 are made of gold, silver, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, aluminum, molybdenum, titanium, indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), or the like.
  • the first electrode 12 and the second electrode 15 may be circuit electrodes or bump electrodes. At least one of the first electrode 12 and the second electrode 15 may be a bump electrode. In FIG. 2, the second electrode 15 is a bump electrode.
  • the circuit connection portion 17 is formed of the adhesive film 1 described above.
  • the circuit connection portion 17 is made of, for example, a cured product of the adhesive film 1.
  • the circuit connection portion 17 is located, for example, on the side of the first circuit member 13 in the direction in which the first circuit member 13 and the second circuit member 16 face each other (hereinafter referred to as “opposite direction”).
  • the first region 18 made of a cured product of components (A), (B) and the like other than the conductive particles 4 of the curable composition of the present invention and the second circuit member 16 in the opposing direction interposed between the second region 19 formed of the cured product of the above-mentioned second curable composition containing the component a), the component (b) and the like, and at least the first electrode 12 and the second electrode 15 And conductive particles 4 electrically connecting the first electrode 12 and the second electrode 15 to each other.
  • the circuit connection portion may not have two regions like the first region 18 and the second region 19 and, for example, components other than the conductive particles 4 of the first curable composition described above.
  • the cured product and the cured product of the second curable composition described above may be mixed.
  • FIG. 3 is a schematic cross-sectional view showing a method of manufacturing the circuit connection structure 10.
  • the method of manufacturing the circuit connection structure 10 is, for example, between the first circuit member 13 having the first electrode 12 and the second circuit member 16 having the second electrode 15.
  • a first circuit including the first circuit board 11 and the first electrode 12 formed on the major surface 11 a of the first circuit board 11.
  • a member 13 and a second circuit member 16 provided with a second circuit board 14 and a second electrode 15 formed on the major surface 14 a of the second circuit board 14 are prepared.
  • the first circuit member 13 and the second circuit member 16 are disposed such that the first electrode 12 and the second electrode 15 face each other, and the first circuit member 13 and the second circuit member 16 are disposed.
  • the adhesive film 1 is disposed between the circuit member 16 and the same.
  • the adhesive film 1 is laminated on the first circuit member 13 so that the first adhesive layer 2 side faces the mounting surface 11 a of the first circuit member 13.
  • the first adhesive film 1 is laminated so that the first electrode 12 on the first circuit board 11 and the second electrode 15 on the second circuit board 14 face each other.
  • the second circuit member 16 is disposed on the circuit member 13.
  • the adhesive film 1 may be laminated on the second circuit member 16 so that the first adhesive layer 2 side faces the mounting surface 14 a of the second circuit member 16.
  • the second adhesive film 1 is laminated such that the first electrode 12 on the first circuit board 11 and the second electrode 15 on the second circuit board 14 face each other.
  • the first circuit member 13 is disposed on the circuit member 16.
  • the 1st circuit member 13 and the 2nd circuit member 16 are heated, heating the 1st circuit member 13, the adhesive film 1, and the 2nd circuit member 16 By pressing in the thickness direction, the first circuit member 13 and the second circuit member 16 are thermocompression-bonded to each other.
  • the second adhesive layer 3 flows so as to fill the gaps between the second electrodes 15 and 15 and is hardened by the above-mentioned heating.
  • the first electrode 12 and the second electrode 15 are electrically connected to each other through the conductive particles 4, and the first circuit member 13 and the second circuit member 16 are bonded to each other, as shown in FIG.
  • the circuit connection structure 10 shown in 2 is obtained.
  • the first circuit is performed by applying pressure and light irradiation or applying pressure and heat and light irradiation, instead of thermocompression bonding by heating.
  • the member 13 and the second circuit member 16 may be joined.
  • FIG. 4 is a perspective view showing an adhesive film storage set of one embodiment.
  • the adhesive film housing set 20 includes an adhesive film 1 for circuit connection, a reel 21 on which the adhesive film 1 is wound, and a housing member 22 for housing the adhesive film 1 and the reel 21. And.
  • the adhesive film 1 is, for example, in the form of a tape.
  • the tape-like adhesive film 1 is produced, for example, by cutting out a sheet-like raw fabric into a long sheet having a width according to the application.
  • a base material may be provided on one side of the adhesive film 1.
  • base materials such as a PET film mentioned above, can be used.
  • the reel 21 includes a first side plate 24 having a core 23 around which the adhesive film 1 is wound, and a second side plate 25 disposed to face the first side plate 24 with the core 23 interposed therebetween. Prepare.
  • the first side plate 24 is a disk made of, for example, plastic, and a central portion of the first side plate 24 is provided with an opening having a circular cross section.
  • the core 23 of the first side plate 24 is a portion around which the adhesive film 1 is wound.
  • the winding core 23 is made of, for example, plastic, and has an annular shape with a thickness similar to the width of the adhesive film 1.
  • the winding core 23 is fixed to the inner side surface of the first side plate 24 so as to surround the opening of the first side plate 24.
  • a shaft hole 26 which is a portion into which a rotation shaft of a winding device or a feeding device (not shown) is inserted.
  • the second side plate 25 is, for example, a disc made of plastic, and the central portion of the second side plate 25 has a circular cross section having the same diameter as the opening of the first side plate 24. Opening is provided.
  • the housing member 22 has, for example, a bag-like shape, and houses the adhesive film 1 and the reel 21.
  • the housing member 22 has an insertion port 27 for housing (inserting) the adhesive film 1 and the reel 21 inside the housing member 22.
  • the housing member 22 has a visual recognition unit 28 which makes the inside of the housing member 22 visible from the outside.
  • the housing member 22 shown in FIG. 4 is configured such that the entire housing member 22 serves as the viewing portion 28.
  • the viewing unit 28 has transparency to visible light.
  • the wavelength width is 50 nm, with an average value of the light transmittance of 30% or more between the wavelengths of 450 to 750 nm.
  • the light transmittance of the visual recognition unit 28 can be obtained by preparing a sample in which the visual recognition unit 28 is cut to a predetermined size, and measuring the light transmission of the sample using an ultraviolet-visible spectrophotometer. Since the housing member 22 has such a visual recognition unit 28, various information such as the product name, lot number, expiration date, etc. affixed to, for example, the reel 21 inside the housing member 22 is also confirmed from the outside of the housing member 22 be able to. This can be expected to prevent the mixing of different products and to improve the efficiency of the sorting operation.
  • the transmittance of light with a wavelength of 365 nm in the visual recognition unit 28 is 10% or less. Since the transmittance of light with a wavelength of 365 nm in the visual recognition unit 28 is 10% or less, light incident from the outside to the inside of the housing member 22 when a photopolymerization initiator is used as the component (B), and the first It is possible to suppress the curing of the second curable composition due to the photopolymerization initiator remaining in the adhesive layer 2. As a result, peeling between the circuit member and the circuit connection portion is likely to occur in a high temperature and high humidity environment, and the reduction effect of the capture rate and the reduction of the fluidity are the reduction effect of the connection resistance of the adhesive film. It is possible to suppress the occurrence of problems such as decrease.
  • the transmittance of light with a wavelength of 365 nm in the visible portion 28 is preferably 10% or less, more preferably 5% or less, and further preferably Is 1% or less, particularly preferably 0.1% or less.
  • the maximum value of the light transmittance in the wavelength range in which radicals, cations or anions can be generated from the above-mentioned photopolymerization initiator (component (B)) in the visible portion 28 is preferably It is at most 10%, more preferably at most 5%, further preferably at most 1%, particularly preferably at most 0.1%.
  • the maximum value of the light transmittance at a wavelength of 254 to 405 nm in the visible portion 28 is preferably 10% or less, more preferably 5% or less, still more preferably 1% or less, particularly preferably 0.1% It is below.
  • the viewing portion 28 (the housing member 22) is formed of, for example, a sheet having a thickness of 10 to 5000 ⁇ m.
  • seat is comprised with the material from which the transmittance
  • a material may consist of one kind of component, and may consist of two or more kinds of components. Examples of the material include low density polyethylene, linear low density polyethylene, polycarbonate, polyester, acrylic resin, polyamide, glass and the like. These materials may contain an ultraviolet absorber.
  • the viewing portion 28 may have a laminated structure formed by laminating a plurality of layers different in light transmittance. In this case, each layer constituting the visual recognition unit 28 may be made of the above-described material.
  • the insertion port 27 may be sealed by being closed by, for example, a sealing machine or the like in order to prevent the entry of air from the outside upon storage. In this case, it is preferable to suction and remove the air in the housing member 22 before closing the insertion opening 27. It is expected that the moisture in the housing member 22 will be reduced from the initial stage of housing and that the entry of air from the outside can be prevented. Further, when the inner surface of the housing member 22 and the reel 21 are in close contact with each other, the inner surface of the housing member 22 and the surface of the reel 21 are rubbed by vibration during transportation to generate foreign matter, and the side plate 24 of the reel 21 , 25 can be prevented from being damaged on the outer surface.
  • the housing member is configured such that the entire housing member is the visual recognition unit, but in another embodiment, the housing member has the visual recognition unit in a part of the housing member. It is also good.
  • the housing member may have a rectangular visible portion substantially at the center of the side surface of the housing member. In this case, the portion other than the visible portion of the housing member may have a black color, for example, so as not to transmit ultraviolet light and visible light.
  • the accommodating member may be box-shaped, for example. It is preferable that the storage member has a cut for opening. In this case, the opening operation at the time of use becomes easy.
  • the weight average molecular weight was measured from a gel permeation chromatograph (GPC) using a calibration curve with standard polystyrene according to the following conditions.
  • Measurement condition Device: Tosoh Corp. GPC-8020 Detector: RI-8020 manufactured by Tosoh Corporation Column: Hitachi Chemical Co., Ltd. Gelpack GLA160S + GLA150S Sample concentration: 120 mg / 3 mL Solvent: Tetrahydrofuran Injection volume: 60 ⁇ L Pressure: 2.94 ⁇ 10 6 Pa (30 kgf / cm 2 ) Flow rate: 1.00 mL / min
  • conductive particles On the surface of polystyrene particles, a layer made of nickel was formed to have a layer thickness of 0.2 ⁇ m. Thus, conductive particles having an average particle diameter of 4 ⁇ m, a maximum particle diameter of 4.5 ⁇ m, and a specific gravity of 2.5 were obtained.
  • A1 dicyclopentadiene type diacrylate (trade name: DCP-A, manufactured by Toagosei Co., Ltd.)
  • A2 Polyurethane acrylate (UA1) synthesized as described above
  • A3 2-methacryloyloxyethyl acid phosphate (trade name: light ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.)
  • B1 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (trade name: Irgacure (registered trademark) OXE01, manufactured by BASF)
  • B2 Benzoyl peroxide (trade name: Niper BMT-K40, manufactured by NOF Corporation)
  • C1 Conductive particles (thermoplastic resin) produced as described above
  • D1 Bisphenol A type phenoxy resin (trade name: PKHC,
  • varnish (varnish composition) of second curable composition As polymerizable compounds a1 to a3, polymerization initiator b1, thermoplastic resin d1, coupling agent e1, filler f1 and solvent g1, polymerizable compounds A1 to A3 in the first curable composition, polymerization initiator B2,
  • the varnish of the second curable composition 1 is prepared using the same components as the thermoplastic resin D1, the coupling agent E1, the filler F1 and the solvent G1 in the amounts (parts by mass) shown in Table 2.
  • content (volume%) of the filler of Table 2 is content based on the whole volume of a 2nd curable composition.
  • Example 1 [Preparation of First Adhesive Film]
  • the varnish of the first curable composition 1 was applied onto a 50 ⁇ m-thick PET film using a coating apparatus. Next, hot air drying was performed at 70 ° C. for 3 minutes to form a layer made of the first curable composition 1 having a thickness (thickness after drying) of 2 ⁇ m on a PET film. Next, the layer formed of the first curable composition 1 was irradiated with light using a metal halide lamp so that the integrated light amount would be 2000 mJ / cm 2 , to polymerize the polymerizable compound. Thus, the first curable composition 1 was cured to form a first adhesive layer.
  • a first adhesive film provided with a 2 ⁇ m-thick first adhesive layer on a PET film was obtained.
  • the conductive particle density at this time was about 7000 pcs / mm 2 .
  • the thickness of the first adhesive layer was measured using a laser microscope OLS4100 manufactured by Olympus Corporation.
  • Second Adhesive Film The varnish of the second curable composition 1 was applied onto a 50 ⁇ m-thick PET film using a coating apparatus. Next, hot air drying was performed at 70 ° C. for 3 minutes to form a second adhesive layer (a layer made of the second curable composition 1) having a thickness of 10 ⁇ m on the PET film. By the above operation, the second adhesive film provided with the second adhesive layer on the PET film was obtained.
  • the DSC calorific value (DSC calorific value Cx) of the first adhesive layer was 36 J / g.
  • the DSC calorific value (DSC calorific value Cy) of the second adhesive layer was 120 J / g. From these results, the DSC calorific value ratio (Cx / Cy) was 0.30.
  • connection structure 1 comprising a circuit connecting portion (connecting structure 1), and to produce a circuit connection structure 2 (connection structure 2).
  • the adhesive film for circuit connection was arrange
  • connection resistance value was determined as an average value of 16 resistances between opposing electrodes. The results are shown in Table 3.
  • connection appearance after the high temperature high humidity test of the obtained circuit connection structure 2 was observed using an optical microscope, and peeling evaluation was performed. Specifically, the area (peeling area) in which peeling occurred between the glass substrate and the circuit connection portion was measured from the glass substrate with thin film electrode side.
  • the high temperature and high humidity test was conducted by leaving it for 200 hours in a constant temperature and humidity chamber at 85 ° C. and 85% RH. The results are shown in Table 3.
  • the produced substrate-attached circuit connecting adhesive film was slit at 0.6 mm to obtain a tape-like substrate-attached adhesive film.
  • An adhesive tape reel including a side plate was prepared, and the tape-like adhesive film with a base material was wound around the adhesive tape reel with the surface on the adhesive film side facing inside. As described above, an adhesive reel was obtained in which a substrate-attached adhesive film having a length of 50 m and a width of 0.6 mm was wound around a core.
  • the obtained adhesive reel was left to stand in a thermostat at 30 ° C. for 24 hours, and then it was checked whether the adhesive film could be pulled out without any problem.
  • the case where it pulled out without problems was A, and the case where problems such as sticking to the substrate (blocking) occurred when drawing out was B, and was evaluated.
  • the results are shown in Table 3.
  • Example 2 The first curable composition 2 is used in place of the first curable composition 1 and, in the preparation of the first adhesive film, the first curable composition is used instead of light irradiation.
  • An adhesive film for circuit connection and a circuit connection structure are produced in the same manner as in Example 1 except that the layer made of Material 2 is cured by heating at 100 ° C. for 180 minutes. Then, measurement of DSC calorific value, evaluation of capture rate, evaluation of connection resistance, peeling evaluation and blocking resistance evaluation were performed. The results are shown in Table 3.
  • Example 3 The first curable composition 3 was used in place of the first curable composition 1, and the first curable composition 3 was used in place of light irradiation in the preparation of the first adhesive film.
  • the layer of the second curable composition 3 was cured by heating at 100 ° C. for 180 minutes, and the varnish of the first curable composition 3 was applied to a thickness of 3 ⁇ m, and conductivity in the first adhesive film
  • An adhesive film for circuit connection and a circuit connection structure were produced in the same manner as in Example 1 except that the particle density was 3000 pcs / mm 2 , and in the same manner as in Example 1, measurement of DSC calorific value , Evaluation of capture rate, evaluation of connection resistance, evaluation of peeling, and evaluation of blocking resistance. The results are shown in Table 3.
  • Example 4 The first curable composition 4 was used in place of the first curable composition 1, and the first curable composition 4 was used in place of light irradiation in the preparation of the first adhesive film.
  • the layer consisting of the above is cured by heating at 100.degree. C. for 180 minutes, the varnish of the first curable composition 4 is applied to a thickness of 1 .mu.m, and the first adhesive film is filled.
  • An adhesive film for circuit connection and a circuit connection structure were produced in the same manner as in Example 1 except that the conductive particle density was 10000 pcs / mm 2 . Measurement, evaluation of capture rate, evaluation of connection resistance, evaluation of peeling, and evaluation of blocking resistance were performed. The results are shown in Table 3.
  • the first curable composition 2 is used in place of the first curable composition 1 and, in the preparation of the first adhesive film, the first curable composition is used instead of light irradiation.
  • An adhesive film for circuit connection and a circuit connection structure are produced in the same manner as in Example 1 except that the layer made of Material 2 is cured by heating at 60 ° C. for 30 minutes. Then, measurement of DSC calorific value, evaluation of capture rate, evaluation of connection resistance, peeling evaluation and blocking resistance evaluation were performed. The results are shown in Table 4.
  • the first curable composition 2 was used in place of the first curable composition 1, and the first curable composition 2 was used in place of light irradiation in the preparation of the first adhesive film. And curing the layer comprising the second curable composition 1 at 100 ° C. for 180 minutes during the preparation of the second adhesive film.
  • An adhesive film for circuit connection and a circuit connection structure are prepared in the same manner as in Example 1 except that curing is carried out by performing the measurement. Measurement of DSC calorific value, capture rate in the same manner as in Example 1 Evaluation, evaluation of connection resistance, peeling evaluation and blocking resistance evaluation were performed. The results are shown in Table 4.
  • SYMBOLS 1 Adhesive film for circuit connection, 2 ... 1st adhesive layer, 3 ... 2nd adhesive layer, 4 ... Conductive particle, 10 ... Circuit connection structure, 12 ... Circuit electrode (1st electrode), 13 ... 1st circuit member, 15 ... bump electrode (2nd electrode), 16 ... 2nd circuit member, 20 ... adhesive film accommodation set, 22 ... accommodation member, 28 ... visual recognition part.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Wire Bonding (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
  • Combinations Of Printed Boards (AREA)

Abstract

L'invention concerne un film adhésif (1) pour connexion de circuits, lequel comporte une première couche (2) d'adhésif contenant des particules conductrices (4) et une deuxième couche (3) d'adhésif stratifiée sur la première couche (2) d'adhésif. Le rapport entre la valeur calorifique ACD de la première couche (2) d'adhésif et la valeur calorifique ACD de la deuxième couche (3) d'adhésif est inférieur ou égal à 0,4.
PCT/JP2018/033290 2017-09-11 2018-09-07 Film adhésif pour connexion de circuits et procédé de fabrication associé, procédé de fabrication d'une structure de connexion de circuits et ensemble contenant pour film adhésif WO2019050012A1 (fr)

Priority Applications (4)

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KR1020207006845A KR102569980B1 (ko) 2017-09-11 2018-09-07 회로 접속용 접착제 필름 및 그의 제조 방법, 회로 접속 구조체의 제조 방법, 그리고 접착제 필름 수용 세트
JP2019541034A JP7210846B2 (ja) 2017-09-11 2018-09-07 回路接続用接着剤フィルム及びその製造方法、回路接続構造体の製造方法、並びに、接着剤フィルム収容セット
KR1020237028180A KR20230126743A (ko) 2017-09-11 2018-09-07 회로 접속용 접착제 필름 및 그의 제조 방법, 회로접속 구조체의 제조 방법, 그리고 접착제 필름 수용 세트
CN201880058646.1A CN111094487A (zh) 2017-09-11 2018-09-07 电路连接用粘接剂膜及其制造方法、电路连接结构体的制造方法、以及粘接剂膜收纳组件

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022102573A1 (fr) * 2020-11-10 2022-05-19 昭和電工マテリアルズ株式会社 Film adhésif pour connexion de circuit et son procédé de production, et structure de connexion de circuit et son procédé de production
WO2023106400A1 (fr) * 2021-12-10 2023-06-15 株式会社レゾナック Film adhésif pour connexion de circuit et structure de connexion de circuit et procédé de fabrication associé

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