WO2023106400A1 - 回路接続用接着剤フィルム、並びに回路接続構造体及びその製造方法 - Google Patents

回路接続用接着剤フィルム、並びに回路接続構造体及びその製造方法 Download PDF

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WO2023106400A1
WO2023106400A1 PCT/JP2022/045456 JP2022045456W WO2023106400A1 WO 2023106400 A1 WO2023106400 A1 WO 2023106400A1 JP 2022045456 W JP2022045456 W JP 2022045456W WO 2023106400 A1 WO2023106400 A1 WO 2023106400A1
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Prior art keywords
adhesive layer
circuit
component
adhesive film
adhesive
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PCT/JP2022/045456
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English (en)
French (fr)
Japanese (ja)
Inventor
和也 成冨
剛幸 市村
孝 中澤
敏光 森谷
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株式会社レゾナック
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Priority to CN202280091030.0A priority Critical patent/CN118786194A/zh
Priority to KR1020247022377A priority patent/KR20240118833A/ko
Priority to JP2023566384A priority patent/JPWO2023106400A1/ja
Publication of WO2023106400A1 publication Critical patent/WO2023106400A1/ja

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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07 e.g. sealing of a cap to a base of a container
    • H01L21/60—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • H05K1/144—Stacked arrangements of planar printed circuit boards
    • 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
    • H05K3/36—Assembling printed circuits with other 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
    • H05K3/36—Assembling printed circuits with other printed circuits
    • H05K3/368—Assembling printed circuits with other printed circuits parallel to each other
    • 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
    • C09J2301/314—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 the adhesive layer and/or the carrier being conductive

Definitions

  • the present disclosure relates to a circuit connection adhesive film, a circuit connection structure, and a method for manufacturing the same.
  • liquid crystal display panels, organic EL panels, etc. have been used as various display means for televisions, PC monitors, mobile phones, smart phones, etc.
  • COG chip on glass
  • a driving IC is directly mounted on the glass substrate of the display panel, is adopted from the viewpoint of finer pitch, lighter weight, and the like.
  • a semiconductor element such as a liquid crystal driving IC is connected on a transparent substrate (such as a glass substrate) having a plurality of transparent electrodes (such as ITO (indium tin oxide)).
  • a transparent substrate such as a glass substrate
  • transparent electrodes such as ITO (indium tin oxide)
  • a circuit-connecting adhesive film having conductive particles dispersed in an adhesive and having anisotropic conductivity is used.
  • the liquid crystal driving IC has a plurality of electrode terminals corresponding to transparent electrodes on its mounting surface, and an adhesive for circuit connection having anisotropic conductivity is used.
  • a flexible plastic substrate such as a polyimide substrate
  • various electronic components such as a driving IC are also mounted on the plastic substrate.
  • COP chip on plastic
  • connection resistance between circuits tends to decrease as the resin fluidity of the adhesive film increases.
  • high resin fluidity means that conductive particles also flow easily at the same time. Poor connection may occur.
  • the adhesive component of the circuit-connecting adhesive film may be cured by heat or light to reduce the fluidity of the conductive particles before the manufacturing process of the circuit-connecting adhesive film or circuit connection. being considered.
  • the ability to remove the resin in the adhesive component is also lowered, which may increase the connection resistance of the circuit connection structure.
  • the adhesive film for circuit connection used for COP mounting is required to have both excellent trapping properties of conductive particles and enhanced resin expulsion properties to reduce the connection resistance of the circuit connection structure. It is
  • the present disclosure aims to provide a circuit connection adhesive film that is excellent in trapping of conductive particles between opposing electrodes of a circuit connection structure and capable of reducing the connection resistance of the circuit connection structure. Main purpose.
  • One aspect of the present disclosure relates to an adhesive film for circuit connection.
  • the adhesive film for circuit connection comprises a first adhesive layer containing conductive particles and a second adhesive layer provided on the first adhesive layer.
  • the flow ratio of the first adhesive layer to the second adhesive layer which is calculated by the following procedures (A1) to (A4), is 0.30 to 0.80. be. According to studies by the inventors of the present disclosure, when the flow ratio is 0.30 or more, the connection resistance of the circuit connection structure can be sufficiently reduced, and when the flow ratio is 0.80 or less, It has been found that there is a tendency for the trapping of conductive particles between the opposing electrodes of the circuit connection structure to be excellent.
  • the circuit-connecting adhesive film is punched out in the thickness direction with the substrates attached to both main surfaces of the circuit-connecting adhesive film to obtain a circular evaluation adhesive film.
  • A2 After peeling the substrate on the side of the first adhesive layer from the adhesive film for evaluation, the adhesive film for evaluation is placed on a glass plate having a thickness of 0.15 mm from the first adhesive layer side. , a pressure bonding temperature of 60° C., a pressure bonding pressure of 10 MPa, and a pressure bonding time of 0.1 second to obtain a temporarily fixed body.
  • the adhesive film for circuit connection is a first adhesive layer containing conductive particles, a cured product of a photocurable resin component, and a first thermosetting resin component, and a first adhesive layer a second adhesive layer disposed thereon and containing a second thermosetting resin component.
  • the photocurable resin component contains a radically polymerizable compound and a photoradical polymerization initiator. Radically polymerizable compounds include polyfunctional (meth)acrylates. By including a polyfunctional (meth)acrylate in the radically polymerizable compound, it is possible to sufficiently reduce the connection resistance of the circuit connection structure while having excellent scavenging properties of the conductive particles between the opposing electrodes of the circuit connection structure. It becomes possible.
  • the thickness of the first adhesive layer may be 5.0 ⁇ m or less, and at this time, the ratio of the thickness of the first adhesive layer to the average particle size of the conductive particles is 0.50 or more. good.
  • the adhesive film for circuit connection of the present disclosure can be mounted at a low pressure (for example, an area conversion pressure of 10 to 50 MPa at the bump electrode), and can be suitably used for COP mounting.
  • the monodispersity of the conductive particles in the circuit connection adhesive film may be 90% or more.
  • the monodispersity ratio means the ratio of conductive particles present in a state (monodisperse state) separated from other conductive particles.
  • the first thermosetting resin component and the second thermosetting resin component may contain a cationic polymerizable compound and a thermal cationic polymerization initiator.
  • the first thermosetting resin component and the second thermosetting resin component have cationic curability
  • the photocurable resin component has radical curability.
  • cationic active species remain when the cured product of the photocurable resin component is formed. It is believed that this is because the curing reaction of the second thermosetting resin component in the second adhesive layer proceeds due to the cationic active species and the expulsion of the resin decreases. . Therefore, if the photocurable resin component has radical curability, cationic active species are not generated when the cured product of the photocurable resin component is formed. It is expected that the progress of the curing reaction of the thermosetting resin component can be suppressed, the deterioration of the expulsion of the resin can be suppressed, and the connection resistance can be reduced.
  • the cationically polymerizable compound may be at least one selected from the group consisting of oxetane compounds and alicyclic epoxy compounds.
  • the thermal cationic polymerization initiator may be a salt compound having an anion containing boron as a constituent element.
  • the circuit-connecting adhesive film may further comprise a third adhesive layer provided on the opposite side of the first adhesive layer to the second adhesive layer.
  • the third adhesive layer may contain a third thermosetting resin component, and the third thermosetting resin component may contain a cationic polymerizable compound and a thermal cationic polymerization initiator. .
  • the method for manufacturing the circuit connection structure includes interposing the circuit connection adhesive film between a first circuit member having a first electrode and a second circuit member having a second electrode, Thermocompression bonding the first circuit member and the second circuit member to electrically connect the first electrode and the second electrode to each other.
  • the circuit connection structure is arranged between a first circuit member having a first electrode, a second circuit member having a second electrode, and the first circuit member and the second circuit member, and a circuit connection portion electrically connecting the first electrode and the second electrode to each other.
  • the circuit connecting part contains the cured body of the circuit connecting adhesive film.
  • the present disclosure provides the circuit connection adhesive film according to [1] to [5], the method for producing the circuit connection structure according to [6], and the circuit connection structure according to [7].
  • [1] A first adhesive layer containing conductive particles and a second adhesive layer provided on the first adhesive layer, and calculated according to the following procedures (A1) to (A4) wherein the flow ratio of said first adhesive layer to said second adhesive layer is between 0.30 and 0.80.
  • (A1) The circuit-connecting adhesive film is punched out in the thickness direction in a state in which the substrates are attached to both main surfaces of the circuit-connecting adhesive film, thereby forming a disk-shaped evaluation adhesive film. obtain.
  • the adhesive film for evaluation is peeled from the first adhesive layer side onto a glass sheet having a thickness of 0.15 mm. It is placed on a plate and thermocompression is performed under the conditions of a compression temperature of 60° C., a compression pressure of 10 MPa, and a compression time of 0.1 second to obtain a temporarily fixed body.
  • A3 After peeling the base material from the temporary fixing body, a glass plate having a thickness of 0.15 mm was placed on the second adhesive layer, and a pressure bonding temperature of 170 ° C., a pressure pressure of 60 MPa, and a pressure bonding time of 5 seconds were applied.
  • the thickness of the first adhesive layer is 5.0 ⁇ m or less, and the ratio of the thickness of the first adhesive layer to the average particle diameter of the conductive particles is 0.50 or more.
  • a circuit connection structure comprising a step of electrically connecting the first electrode and the second electrode to each other by thermocompression bonding the first circuit member and the second circuit member with a film interposed. manufacturing method. [7] a first circuit member having a first electrode; a second circuit member having a second electrode; A circuit connecting portion electrically connecting the first electrode and the second electrode to each other, wherein the circuit connecting portion cures the adhesive film for circuit connection according to any one of [1] to [5].
  • a circuit-connected structure including a body.
  • a circuit-connecting adhesive film is disclosed that is excellent in trapping of conductive particles between opposing electrodes of a circuit-connecting structure and capable of reducing the connection resistance of the circuit-connecting structure.
  • Such a circuit-connecting adhesive film can be mounted at a low pressure (for example, an area-converted pressure of 10 to 50 MPa at the bump electrode), and can be suitably used for COP mounting.
  • a circuit connection structure using such an adhesive film for circuit connection and a method for manufacturing the same are disclosed.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of an adhesive film for circuit connection.
  • FIG. 2 is a schematic cross-sectional view showing another embodiment of an adhesive film for circuit connection.
  • FIG. 3 is a schematic cross-sectional view of a substrate used for manufacturing the circuit-connecting adhesive film of FIG.
  • FIG. 4 is a diagram showing a state in which conductive particles are arranged in the recesses of the base shown in FIG. 5(a) and 5(b) are schematic cross-sectional views showing one step of the method for producing the circuit-connecting adhesive film of FIG. 6(a) and 6(b) are schematic cross-sectional views showing one step of the method for producing the circuit-connecting adhesive film of FIG.
  • FIG. 7 is a schematic cross-sectional view showing one embodiment of the circuit connection structure.
  • 8A and 8B are schematic cross-sectional views showing an embodiment of a method for manufacturing a circuit connection structure.
  • the numerical range indicated using “-” indicates the range including the numerical values before and after "-" as the minimum and maximum values, respectively.
  • the upper limit value or lower limit value of the numerical range at one step may be replaced with the upper limit value or lower limit value of the numerical range at another step.
  • the upper and lower limits of the numerical ranges may be replaced with the values shown in the examples.
  • the upper limit value and the lower limit value described individually can be combined arbitrarily.
  • both numerical values A and B are included in the numerical range as lower and upper limits, respectively.
  • the description “10 or more” means “10” and “a numerical value exceeding 10”, and this applies even when the numerical values are different.
  • the description “10 or less” means “10” and “a numerical value less than 10”, and this applies even if the numerical values are different.
  • “(meth)acrylate” means at least one of acrylate and methacrylate corresponding thereto. The same applies to other similar expressions such as “(meth)acryloyl” and “(meth)acrylic acid”.
  • “A or B” may include either one of A and B, or may include both. Materials exemplified below may be used singly or in combination of two or more unless otherwise specified.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition.
  • the adhesive film for circuit connection comprises a first adhesive layer containing conductive particles and a second adhesive layer provided on the first adhesive layer.
  • the flow ratio of the first adhesive layer to the second adhesive layer which is calculated by the following procedures (A1) to (A4), is 0.30 to 0.80. be.
  • a circuit-connecting adhesive film is punched out in the thickness direction with substrates attached to both main surfaces of the circuit-connecting adhesive film to obtain a disk-shaped evaluation adhesive film. .
  • A2 After peeling the substrate on the side of the first adhesive layer from the adhesive film for evaluation, the adhesive film for evaluation is placed on a glass plate having a thickness of 0.15 mm from the first adhesive layer side.
  • a pressure bonding temperature of 60° C., a pressure bonding pressure of 10 MPa, and a pressure bonding time of 0.1 second was obtained by peeling off the base material from the temporarily fixed body.
  • a glass plate having a thickness of 0.15 mm was placed on the second adhesive layer, and under the conditions of a pressure bonding temperature of 170 ° C., a pressure pressure of 60 MPa, and a pressure bonding time of 5 seconds. It is heat-pressed to obtain a press-bonded body.
  • the adhesive film for circuit connection is a first adhesive layer containing conductive particles, a cured product of a photocurable resin component, and a first thermosetting resin component, and a first adhesive layer a second adhesive layer disposed thereon and containing a second thermosetting resin component.
  • the photocurable resin component contains a radically polymerizable compound and a photoradical polymerization initiator. Radically polymerizable compounds include polyfunctional (meth)acrylates.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the circuit-connecting adhesive film, and is a diagram schematically showing a vertical cross-section of the circuit-connecting adhesive film.
  • the circuit-connecting adhesive film 10A shown in FIG. 1 includes a first adhesive layer 1 containing a plurality of conductive particles 4 and an adhesive component 3, and a second and an adhesive layer 2 of As used herein, the term "longitudinal section” means a section (section in the thickness direction) perpendicular to the main surface (for example, the circuit-connecting adhesive film 10A).
  • At least some of the plurality of conductive particles 4 may be arranged in the horizontal direction in the vertical cross section of the circuit connection adhesive film 10A with adjacent conductive particles separated from each other.
  • the circuit-connecting adhesive film 10A in its vertical cross-section, has a central region 10a in which the conductive particles 4 are arranged in a horizontal direction separated from the adjacent conductive particles, and the conductive particles 4 are present. It may be configured by surface side regions 10b and 10c that do not.
  • the "horizontal direction” means a direction parallel to the main surface of the circuit-connecting adhesive film (horizontal direction in FIG. 1). In FIG.
  • part of the conductive particles 4 are exposed from the surface of the first adhesive layer 1 (for example, protrude toward the second adhesive layer 2), but the conductive particles 4 are The entire conductive particles 4 may be embedded in the first adhesive layer 1 so as not to be exposed from the surface of the adhesive layer 1 .
  • the conductive particles 4 may be dispersed in the first adhesive layer 1 of the circuit connection adhesive film 10A. Therefore, the circuit-connecting adhesive film 10A can be a circuit-connecting adhesive film having anisotropic conductivity (anisotropically conductive adhesive film).
  • the circuit-connecting adhesive film 10A is interposed between a first circuit member having a first electrode and a second circuit member having a second electrode, so that the first circuit member and the second circuit It may be used to thermocompress members to electrically connect the first electrode and the second electrode to each other.
  • anisotropically conductive means to conduct in the pressurized direction and maintain insulation in the non-pressurized direction.
  • the flow ratio of the first adhesive layer 1 to the second adhesive layer 2 (flow amount of the first adhesive layer 1/flow amount of the second adhesive layer 2) is 0.30 to 0.80. is.
  • the flow ratio is an index indicating the ratio (ratio) of fluidity (flow) during thermocompression bonding of the first adhesive layer 1 to the second adhesive layer 2 .
  • the flow ratio is calculated by the following procedures (A1) to (A4).
  • (A1) The circuit-connecting adhesive film 10A is punched out in the thickness direction in a state in which the substrates are attached to both main surfaces of the circuit-connecting adhesive film 10A, and a disk-shaped evaluation adhesive film is obtained.
  • the adhesive film for evaluation is placed on a glass plate having a thickness of 0.15 mm from the first adhesive layer side. , a pressure bonding temperature of 60° C., a pressure bonding pressure of 10 MPa, and a pressure bonding time of 0.1 second to obtain a temporarily fixed body.
  • A3 After peeling off the base material from the temporarily fixed body, a glass plate having a thickness of 0.15 mm was placed on the second adhesive layer, and under the conditions of a pressure bonding temperature of 170 ° C., a pressure pressure of 60 MPa, and a pressure bonding time of 5 seconds. It is heat-pressed to obtain a press-bonded body.
  • a disk-shaped adhesive film for evaluation is obtained.
  • the disc-shaped adhesive film for evaluation can have a diameter of, for example, 1 mm. Details of the evaluation method are shown in Examples.
  • the connection resistance of the circuit connection structure can be sufficiently reduced, and when the flow ratio is 0.80 or less, It was found that the trapping property of the conductive particles between the facing electrodes of the circuit connection structure is excellent.
  • the flow ratio is 0.30 to 0.80, and from the viewpoint of the connection resistance of the circuit connection structure, 0.35 or more, 0.40 or more, 0.45 or more, 0.50 or more, or 0.55 or more From the viewpoint of the ability to capture conductive particles, it may be 0.78 or less, 0.75 or less, 0.72 or less, 0.70 or less, or 0.68 or less.
  • the flow ratio tends to be easily adjusted within a predetermined range, for example, by containing a polyfunctional (meth)acrylate as a radically polymerizable compound. Also, the flow ratio can be increased by, for example, reducing the number of functional groups of polyfunctional (meth)acrylate (for example, increasing the proportion of bifunctional (meth)acrylate used).
  • the first adhesive layer 1 includes, for example, conductive particles 4 (hereinafter sometimes referred to as "(A) component”) and a photocurable resin component (hereinafter sometimes referred to as “(B) component”). and a thermosetting resin component (hereinafter sometimes referred to as “(C) component”).
  • the cured product of component (B) may be a cured product obtained by completely curing component (B) or a cured product obtained by partially curing component (B).
  • Component (C) is a component that can flow when connected, and is, for example, an uncured curable component (eg, resin component).
  • Components other than the conductive particles 4 that constitute the first adhesive layer 1 are, for example, non-conductive components (eg, insulating resin components).
  • component (A) component conductive particles
  • the component (A) is not particularly limited as long as it is a particle having conductivity, metal particles composed of metals such as Au, Ag, Pd, Ni, Cu, solder, conductive carbon It may be a conductive carbon particle or the like composed of.
  • Component (A) is a coated conductive particle comprising a nucleus containing non-conductive glass, ceramic, plastic (such as polystyrene), etc., and a coating layer containing the metal or the conductive carbon and covering the nucleus, good too.
  • the component (A) one type of various conductive particles may be used alone, or a plurality thereof may be used in combination.
  • the component (A) is preferably formed of a coated conductive particle comprising a core containing plastic and a coating layer containing metal or conductive carbon and covering the core, or a heat-fusible metal. metal particles.
  • the cured product of the thermosetting resin component can be easily deformed by heating or pressing. ) can increase the contact area with the component and further improve the electrical conductivity between the electrodes.
  • the component (A) is metal particles made of a heat-fusible metal, the connection between the electrodes tends to be stronger. This tendency is remarkable when solder particles are used as the component (A).
  • the solder particles may contain at least one selected from the group consisting of tin, tin alloys, indium, and indium alloys from the viewpoint of achieving both connection strength and low melting point.
  • the solder particles are selected from In--Bi alloys, In--Sn alloys, In--Sn--Ag alloys, Sn--Au alloys, Sn-- At least one selected from the group consisting of Bi alloys, Sn--Bi--Ag alloys, Sn--Ag--Cu alloys and Sn--Cu alloys may be included.
  • Component (A) is an insulation-coated conductive particle comprising the metal particles, the conductive carbon particles, or the coated conductive particles, and an insulating material such as a resin, and an insulating layer covering the surface of the particles. good too.
  • the component (A) is an insulating coating conductive particle, even if the content of the component (A) is large, the surface of the particle is provided with an insulating layer, so the short circuit due to the contact between the components (A) The occurrence can be suppressed, and the insulation between adjacent electrode circuits can be improved.
  • the maximum particle size of component (A) must be smaller than the minimum distance between electrodes (the shortest distance between adjacent electrodes).
  • the maximum particle size of component (A) 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 component (A) is 30.0 ⁇ m or less, 25.0 ⁇ m or less, 20.0 ⁇ m or less, 15.0 ⁇ m or less, 10.0 ⁇ m or less, or 5.0 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity.
  • the particle size of the component (A) is the diameter of a circle circumscribing the conductive particles in the SEM image.
  • the average particle size of component (A) may be 1.0 ⁇ m or more, 2.0 ⁇ m or more, 2.5 ⁇ m or more, or 3.0 ⁇ m or more from the viewpoint of excellent dispersibility and conductivity.
  • the average particle diameter of component (A) may be 20.0 ⁇ m or less, 10.0 ⁇ m or less, 7.0 ⁇ m or less, or 5.0 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity.
  • the particle size is measured by observation using a scanning electron microscope (SEM) for any 300 (pcs) of component (A) in the first adhesive layer, and the obtained particle size Let the average value be the average particle size.
  • Component (A) is preferably dispersed uniformly in the first adhesive layer 1 .
  • the particle density of the component (A) in the circuit connection adhesive film 10A is 100 particles/mm 2 or more, 1000 particles/mm 2 or more, 3000 particles/mm 2 or more, 5000 particles. / mm2 or more, 7000/ mm2 or more, 10000/mm2 or more , or 12000/mm2 or more.
  • the particle density of the component (A) in the circuit-connecting adhesive film 10A is 100,000 particles/mm 2 or less, 70,000 particles/mm 2 or less, or 50,000 particles/mm 2 or less, from the viewpoint of improving the insulation between adjacent electrodes. , 30,000/mm 2 or less, or 20,000/mm 2 or less.
  • the monodispersity of the component (A) in the circuit-connecting adhesive film 10A may be 90% or more. When the monodispersity of component (A) is within this range, short-circuit failures between adjacent circuits are less likely to occur, and a circuit connection structure with sufficiently high connection reliability tends to be easily obtained.
  • the monodispersity of component (A) may be 92% or higher, 94% or higher, 96% or higher, 97% or higher, 98% or higher, or 99% or higher.
  • the upper limit of monodispersity can be 100%.
  • the monodispersity is obtained by observing the circuit-connecting adhesive film 10A from the first adhesive layer side at a magnification of 200 using a metallurgical microscope, and measuring the component (A) in the circuit-connecting adhesive film 10A.
  • the number can be measured and obtained according to the following formula.
  • Monodisperse rate (%) (number of monodispersed conductive particles in 2500 ⁇ m 2 / number of conductive particles in 2500 ⁇ m 2 ) x 100
  • the content of component (A) is 1% by mass or more, 5% by mass or more, or 10% 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. It's okay.
  • the content of component (A) may be 60% by mass or less, 50% by mass or less, or 40% by mass or less based on the total mass of the first adhesive layer, from the viewpoint of easily suppressing short circuits.
  • the content of component (A) is within the above range, the effects of the present disclosure tend to be remarkably exhibited.
  • the content of component (A) in the composition or composition layer (based on the total mass of the composition or composition layer) may be the same as the above range.
  • Component (B) Photocurable resin component
  • Component (B) is not particularly limited as long as it is a resin component that cures when irradiated with light.
  • the component may be a radical-curing resin component from the viewpoint of better connection resistance.
  • Component (B) includes, for example, a radically polymerizable compound (hereinafter sometimes referred to as "(B1) component”) and a photoradical polymerization initiator (hereinafter sometimes referred to as "(B2) component”). You can stay.
  • the (B) component can be a component consisting of the (B1) component and the (B2) component.
  • the (B1) component is a compound that polymerizes by radicals generated from the (B2) component by irradiation with light (for example, ultraviolet light).
  • the component (B1) may be either a monomer or a polymer (or oligomer) obtained by polymerizing one or more monomers.
  • (B1) component may be used individually by 1 type, and may be used in combination of plurality.
  • the (B1) component is a compound having a radically polymerizable group that reacts with radicals.
  • radically polymerizable groups include (meth)acryloyl groups, vinyl groups, allyl groups, styryl groups, alkenyl groups, alkenylene groups, maleimide groups and the like.
  • the number of radically polymerizable groups (number of functional groups) of the component (B1) may be 2 or more from the viewpoint of easily obtaining the desired melt viscosity after polymerization and having excellent connection reliability, and the effect of reducing the connection resistance. can be 10 or less, 6 or less, or 4 or less from the viewpoint of further improving the curing shrinkage during polymerization.
  • a compound having the number of radically polymerizable groups outside the above range may also be used in order to balance the crosslink density and cure shrinkage. good.
  • the (B1) component contains a polyfunctional (difunctional or higher) (meth)acrylate from the viewpoint of suppressing the flow of the conductive particles.
  • the polyfunctional (bifunctional or higher) (meth)acrylate may be a bifunctional or trifunctional (meth)acrylate, preferably a bifunctional (meth)acrylate.
  • the bifunctional (meth)acrylate may be a bifunctional aromatic (meth)acrylate.
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate.
  • acrylate propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated polypropylene glycol Di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1 , 10-decanedi
  • the content of the polyfunctional (difunctional or higher) (meth)acrylate is, for example, 50 to 100, based on the total mass of the component (B1), from the viewpoint of achieving both the effect of reducing connection resistance and suppressing particle flow. % by weight, 70 to 100% by weight, or 90 to 100% by weight, or even 100% by weight.
  • the (B1) component may further contain a monofunctional (meth)acrylate in addition to the polyfunctional (bifunctional or higher) (meth)acrylate.
  • Monofunctional (meth)acrylates include, for example, (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate acrylates 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-
  • the content of the monofunctional (meth)acrylate may be, for example, 0 to 50% by mass, 0 to 30% by mass, or 0 to 10% by mass, based on the total mass of the component (B1), and 0 mass %.
  • the cured product of component (B) may have, for example, a polymerizable group that reacts with something other than radicals.
  • Polymerizable groups that react by means other than radicals may be, for example, cationically polymerizable groups that react by means of cations.
  • Examples of cationic polymerizable groups include epoxy groups such as glycidyl groups, alicyclic epoxy groups such as epoxycyclohexylmethyl groups, and oxetanyl groups such as ethyloxetanylmethyl groups.
  • the cured product of the component (B) having a polymerizable group that reacts by means other than radicals is, for example, a (meth)acrylate having an epoxy group, a (meth)acrylate having an alicyclic epoxy group, or a (meth)acrylate having an oxetanyl group. It can be introduced by using a (meth)acrylate having a polymerizable group that reacts by means other than radicals such as (B) as the component (B).
  • (B1) Mass ratio of (meth) acrylate having a polymerizable group that reacts with a non-radical to the total mass of the component (mass of (meth) acrylate having a polymerizable group that reacts with a non-radical (amount charged)/(B1)
  • the total mass (amount charged) of the components may be, for example, 0 to 0.7, 0 to 0.5, or 0 to 0.3 from the viewpoint of improving reliability.
  • the (B1) component may contain other radically polymerizable compounds in addition to polyfunctional (difunctional or higher) and monofunctional (meth)acrylates.
  • Other radically polymerizable compounds include, for example, maleimide compounds, vinyl ether compounds, allyl compounds, styrene derivatives, acrylamide derivatives, nadimide derivatives and the like.
  • the content of other radically polymerizable compounds may be, for example, 0 to 40% by mass based on the total mass of component (B1).
  • Photoradical polymerization initiator Component (B2) is light containing a wavelength within the range of 150 to 750 nm, preferably light containing a wavelength within the range of 254 to 405 nm, more preferably light containing a wavelength of 365 nm. It is a photopolymerization initiator that generates radicals when irradiated with light (for example, ultraviolet light). (B2) component may be used individually by 1 type, and may be used in combination of plurality.
  • (B2) component is decomposed by light to generate free radicals.
  • the (B2) component is a compound that generates radicals upon application of external light energy.
  • Component (B2) has an oxime ester structure, a bisimidazole structure, an acridine structure, an ⁇ -aminoalkylphenone structure, an aminobenzophenone structure, an N-phenylglycine structure, an acylphosphine oxide structure, a benzyldimethylketal structure, and an ⁇ -hydroxyalkylphenone structure. It may be a compound having a structure such as (B2) component may be used individually by 1 type, and may be used in combination of plurality.
  • the component (B2) is selected from the group consisting of an oxime ester structure, an ⁇ -aminoalkylphenone structure, and an acylphosphine oxide structure, from the viewpoint of easily obtaining the desired melt viscosity and from the viewpoint of being more excellent in the effect of reducing connection resistance. It may be a compound having at least one structure of
  • compounds having an oxime ester structure 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-carbazol-3-yl]-, 1-(o-o-
  • compounds having an ⁇ -aminoalkylphenone structure include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -morpholinophenyl)-butanone-1 and the like.
  • compounds having an acylphosphine oxide structure include bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine. oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and the like.
  • the content of component (B2) is, for example, 0.1 to 10 parts by mass, 0.3 to 7 parts by mass, or 0 with respect to 100 parts by mass of component (B1) from the viewpoint of suppressing the flow of conductive particles. .5 to 5 parts by mass.
  • the content of the cured product of component (B) is 1% by mass or more, 5% by mass or more, or 10% by mass or more based on the total mass of the first adhesive layer.
  • the content of the cured product of component (B) is 50% by mass or less, 40% by mass or less, or 30% by mass, based on the total mass of the first adhesive layer, from the viewpoint of expressing low resistance in low-pressure mounting. may be:
  • the content of the cured product of component (B) is within the above range, the effects of the present disclosure tend to be remarkably exhibited.
  • the content of component (B) in the composition or composition layer (based on the total mass of the composition or composition layer) may be the same as the above range.
  • thermosetting resin component is not particularly limited as long as it is a resin component that is cured by heat. may be a cationic curable resin component from the viewpoint of superior connection resistance.
  • Component (C) includes, for example, a cationic polymerizable compound (hereinafter sometimes referred to as "(C1) component”) and a thermal cationic polymerization initiator (hereinafter sometimes referred to as "(C2) component”). You can stay.
  • Component (C) may be a component consisting of component (C1) and component (C2).
  • the first thermosetting resin component, the second thermosetting resin component, and the third thermosetting resin component are the first adhesive layer, the second adhesive layer, and the third thermosetting resin component, respectively.
  • thermosetting resin component contained in the adhesive layer and components contained in the first thermosetting resin component, the second thermosetting resin component, and the third thermosetting resin component (for example, (C1) component, (C2) component, etc.) and contents may be the same or different.
  • (C1) component cationic polymerizable compound
  • the (C1) component is a compound that crosslinks by reacting with the (C2) component by heat.
  • the (C1) component means a compound that does not have a radically polymerizable group that reacts with radicals, and the (C1) component is not included in the (B1) component.
  • (C1) Component includes, for example, compounds having a cyclic ether group such as oxetane compounds and epoxy compounds.
  • (C1) component may be used individually by 1 type, and may be used in combination of plurality.
  • the component (C1) may contain, for example, at least one selected from the group consisting of an oxetane compound and an alicyclic epoxy compound, from the viewpoint of further improving the effect of reducing the connection resistance and improving the connection reliability. .
  • the component (C1) preferably contains both at least one oxetane compound and at least one alicyclic epoxy compound from the viewpoint of easily obtaining a desired melt viscosity.
  • the oxetane compound as the component (C1) can be used without any particular limitation as long as it has an oxetanyl group and does not have a radically polymerizable group.
  • examples of commercially available oxetane compounds include ETERNACOLL OXBP (trade name, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, manufactured by Ube Industries, Ltd.), OXSQ, OXT-121, OXT-221, OXT-101, OXT-212 (trade name, manufactured by Toagosei Co., Ltd.) and the like.
  • One of these compounds may be used alone, or two or more of them may be used in combination.
  • the alicyclic epoxy compound as the (C1) component can be used without particular limitation as long as it has an alicyclic epoxy group (eg, epoxycyclohexyl group) and does not have a radically polymerizable group.
  • Examples of commercially available alicyclic epoxy compounds include EHPE3150, EHPE3150CE, Celoxide 8010, Celoxide 2021P, Celoxide 2081 (trade name, manufactured by Daicel Corporation). One of these compounds may be used alone, or two or more of them may be used in combination.
  • Component (C2) Thermal Cationic Polymerization Initiator
  • the component (C2) is a thermal polymerization initiator that initiates polymerization by generating an acid or the like upon heating.
  • the (C2) component may be a salt compound composed of a cation and an anion.
  • Component (C2) is, for example, BF 4 ⁇ , BR 4 ⁇ (R represents a phenyl group substituted with two or more fluorine atoms or two or more trifluoromethyl groups), PF 6 ⁇ , SbF 6 ⁇ and onium salts such as sulfonium salts, phosphonium salts, ammonium salts (quaternary ammonium salts), diazonium salts, iodonium salts, anilinium salts and pyridium salts having anions such as AsF 6 — . These may be used individually by 1 type, and may be used in combination of plurality.
  • the component (C2) is, for example, an anion containing boron as a constituent element, that is, BF 4 ⁇ or BR 4 ⁇ (R is 2 or more fluorine atoms or 2 or more trifluoromethyl groups). represents a substituted phenyl group).
  • the anion containing boron as a constituent element may be BR 4 — , more specifically tetrakis(pentafluorophenyl)borate.
  • the onium salt as the (C2) component may be, for example, a quaternary ammonium salt or anilinium salt, since it has resistance to substances that can inhibit cationic curing.
  • anilinium salt compounds include N,N-dialkylanilinium salts such as N,N-dimethylanilinium salts and N,N-diethylanilinium salts.
  • the (C2) component may be a quaternary ammonium salt or anilinium salt having an anion containing boron as a constituent element.
  • Commercially available products of such salt compounds include, for example, CXC-1821 (trade name, manufactured by King Industries).
  • the content of component (C2) is, for example, 0.1 to 20 parts by mass, 1 18 parts by weight, 3 to 15 parts by weight, or 5 to 12 parts by weight.
  • the content of component (C) is 5% by mass or more, 10% by mass or more, and 15% by mass, based on the total mass of the first adhesive layer. or more, or 20% by mass or more. From the viewpoint of ensuring the formability of the first adhesive layer, the content of component (C) is 70% by mass or less, 60% by mass or less, and 50% by mass, based on the total mass of the first adhesive layer. or less, or 40% by mass or less.
  • the content of component (C) is within the above range, the effects of the present disclosure tend to be remarkably exhibited.
  • the content of component (C) in the composition or composition layer (based on the total mass of the composition or composition layer) may be the same as the above range.
  • the first adhesive layer 1 may further contain other components in addition to the (A) component, the cured product of the (B) component, and the (C) component.
  • Other components include, for example, a thermoplastic resin (hereinafter sometimes referred to as "(D) component”), a coupling agent (hereinafter sometimes referred to as “(E) component”), a filler (hereinafter sometimes referred to as “(E) component”), , and may be referred to as “(F) component”).
  • component (D) examples include phenoxy resins, polyester resins, polyamide resins, polyurethane resins, polyester urethane resins, acrylic rubbers, and epoxy resins (solid at 25°C). These may be used individually by 1 type, and may be used in combination of plurality.
  • a composition layer (further the first adhesive layer 1) is formed from the composition containing the components (A), (B), and (C) by further containing the component (D). can be easily formed.
  • the (D) component may be, for example, a phenoxy resin.
  • the content of component (D) may be 1% by mass or more, 5% by mass or more, or 10% by mass or more, and 70% by mass or less, or 50% by mass, based on the total mass of the first adhesive layer. or less, or 30% by mass or less.
  • the content of component (D) in the composition or composition layer (based on the total mass of the composition or composition layer) may be the same as the above range.
  • component (E) examples include silane coupling agents having organic functional groups such as (meth)acryloyl groups, mercapto groups, amino groups, imidazole groups and epoxy groups, silane compounds such as tetraalkoxysilanes, and tetraalkoxytitanate derivatives. , polydialkyl titanate derivatives and the like. These may be used individually by 1 type, and may be used in combination of plurality. By including the component (E) in the first adhesive layer 1, the adhesiveness can be further improved.
  • the (E) component may be, for example, a silane coupling agent.
  • the content of component (E) may be 0.1 to 10% by mass based on the total mass of the first adhesive layer.
  • the content of component (E) in the composition or composition layer (based on the total mass of the composition or composition layer) may be the same as the above range.
  • (F) component includes, for example, non-conductive fillers (eg, non-conductive particles).
  • Component may be either an inorganic filler or an organic filler.
  • inorganic fillers include metal oxide fine particles such as silica fine particles, alumina fine particles, silica-alumina fine particles, titania fine particles and zirconia fine particles; and inorganic fine particles such as metal nitride fine particles.
  • organic filler include organic fine particles such as silicone fine particles, methacrylate/butadiene/styrene fine particles, acryl/silicone fine particles, polyamide fine particles, and polyimide fine particles. These may be used individually by 1 type, and may be used in combination of plurality.
  • the (F) component may be silica fine particles, for example.
  • the content of component (F) may be 0.1 to 10% by mass based on the total mass of the first adhesive layer.
  • the content of component (F) in the composition or composition layer (based on the total mass of the composition or composition layer) may be the same as the above range.
  • the first adhesive layer 1 may further contain other additives such as softeners, accelerators, antidegradants, colorants, flame retardants, and thixotropic agents.
  • the content of other additives may be, for example, 0.1 to 10% by mass based on the total mass of the first adhesive layer.
  • the content of other additives in the composition or composition layer (based on the total mass of the composition or composition layer) may be the same as the above range.
  • the thickness d1 of the first adhesive layer 1 may be, for example, 30.0 ⁇ m or less, 20.0 ⁇ m or less, 15.0 ⁇ m or less, 10.0 ⁇ m or less, 8.0 ⁇ m or less, 5.0 ⁇ m or less, 4 .5 ⁇ m or less, 4.0 ⁇ m or less, 3.5 ⁇ m or less, 3.0 ⁇ m or less, or 2.5 ⁇ m or less.
  • the thickness d1 of the first adhesive layer 1 is 30.0 ⁇ m or less, the amount of resin between the opposing circuits is reduced, and an increase in the connection resistance between the opposing circuits can be suppressed. Such a tendency is more pronounced when the thickness d1 of the first adhesive layer 1 is 5.0 ⁇ m or less.
  • the thickness d1 of the first adhesive layer 1 may be, for example, 0.1 ⁇ m or more or 0.7 ⁇ m or more.
  • the first The first adhesive layer 1 and the second adhesive layer 2 located in the spaced part between the adjacent conductive particles 4, 4 are separated from the surface 1a of the adhesive layer 1 opposite to the second adhesive layer 2 side. is the thickness of the first adhesive layer 1, and the exposed portion of the conductive particles 4 is included in the thickness of the first adhesive layer 1.
  • the length of the exposed portion of the conductive particles 4 may be, for example, 0.1 ⁇ m or more and 5.0 ⁇ m or less.
  • the thickness d1 of the first adhesive layer 1 can be obtained, for example, by the method described in Examples. Specifically, the adhesive film for circuit connection is sandwiched between two sheets of glass (thickness: about 1 mm), and 100 g of bisphenol A type epoxy resin (trade name: JER811, manufactured by Mitsubishi Chemical Corporation) and a curing agent (trade name: JER811). Name: Epomount Curing Agent, manufactured by Refinetech Co., Ltd.) After casting with a resin composition consisting of 10 g, the cross section is polished using a polishing machine, and a scanning electron microscope (SEM, trade name: SE-8020, stock manufactured by Hitachi High-Tech Science). Such an operation may be performed multiple times and the average value thereof may be used as the thickness d1 of the first adhesive layer 1 .
  • SEM scanning electron microscope
  • the ratio of the thickness of the first adhesive layer 1 to the average particle size of the conductive particles 4 is 0.50 or more, for example , 0.55 or more, or 0.60 or more.
  • the ratio may be, for example, 2.00 or less, 1.50 or less, 1.20 or less, or 1.00 or less.
  • the second adhesive layer 2 may be, for example, an insulating adhesive layer composed of a non-conductive component (insulating resin component).
  • the second adhesive layer 2 contains at least component (C).
  • the (C1) component and (C2) component used in the (C) component (that is, the second thermosetting resin component) in the second adhesive layer 2 are (C) in the first adhesive layer 1 Since it is the same as the components (C1) and (C2) used in the component (that is, the first thermosetting resin component), detailed description is omitted here.
  • the second thermoset resin component may be the same as or different from the first thermoset resin component.
  • the content of component (C) is 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more based on the total mass of the second adhesive layer.
  • the content of component (C) is 80% by mass or less, 70% by mass or less, based on the total mass of the second adhesive layer, from the viewpoint of preventing resin seepage problems in the reel, which is one mode of the supply form. , 60% by mass or less, or 50% by mass or less.
  • the second adhesive layer 2 may further contain other components and other additives in the first adhesive layer 1. Preferred aspects of other components and other additives are the same as those of the first adhesive layer 1 .
  • the content of component (D) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 60% by mass or less, or 40% by mass, based on the total mass of the second adhesive layer. or less, or 20% by mass or less.
  • the content of component (E) may be 0.1 to 10% by mass based on the total mass of the second adhesive layer.
  • the content of component (F) may be 1% by mass or more, 10% by mass or more, or 30% by mass or more, and 90% by mass or less, or 70% by mass, based on the total mass of the second adhesive layer. or less, or 50% by mass or less.
  • the content of other additives may be, for example, 0.1 to 10% by mass based on the total mass of the second adhesive layer.
  • the thickness d2 of the second adhesive layer 2 may be appropriately set according to the height of the electrodes of the circuit members to be adhered.
  • the thickness d2 of the second adhesive layer 2 is 5.0 ⁇ m or more or 7 ⁇ m or more from the viewpoint of sufficiently filling the space between the electrodes to seal the electrodes and obtaining better connection reliability. 0 ⁇ m or more, and may be 30.0 ⁇ m or less, 20.0 ⁇ m or less, 15.0 ⁇ m or less, or 13.0 ⁇ m or less.
  • the first adhesive layer 2 when a part of the conductive particles 4 is exposed from the surface of the first adhesive layer 1 (for example, protruding to the second adhesive layer 2 side), the first The distance from the surface 2a opposite to the adhesive layer 1 side to the boundary S between the first adhesive layer 1 and the second adhesive layer 2 located in the spaced portion between the adjacent conductive particles 4, 4 ( The distance indicated by d2 in FIG. 1) is the thickness of the second adhesive layer 2 .
  • the thickness d2 of the second adhesive layer 2 can be obtained, for example, in the same manner as the thickness d1 of the first adhesive layer 1 described above.
  • the thickness of the circuit-connecting adhesive film 10A (total thickness of all layers constituting the circuit-connecting adhesive film 10A; in FIG. 1, the thickness d1 of the first adhesive layer 1 and the thickness of the second The total thickness d2 of the adhesive layer 2) may be, for example, 5.0 ⁇ m or more or 8.0 ⁇ m or more, 60.0 ⁇ m or less, 40.0 ⁇ m or less, 30.0 ⁇ m or less, or 20.0 ⁇ m or less. It's okay.
  • the circuit-connecting adhesive film 10A is an adhesive film used for circuit connection.
  • the circuit-connecting adhesive film 10A may or may not have anisotropic conductivity. That is, the circuit-connecting adhesive film may be an anisotropically conductive adhesive film or a non-anisotropically conductive (for example, isotropically conductive) adhesive film.
  • the circuit-connecting adhesive film 10A includes a first circuit member having a first electrode (the surface on which the first electrode is provided) and a second circuit member having the second electrode (the The surface on which the second electrode is provided), and the first circuit member and the second circuit member are thermocompression bonded (the first circuit member, the circuit connection adhesive film 10A, and The laminate including the second circuit member is heated while being pressed in the thickness direction of the laminate), and the first electrode and the second electrode are connected (via the conductive particles (or the melted and solidified conductive particles) ) may be used to electrically connect to each other.
  • thermosetting resin component secures the expulsion of the resin at the time of connection, while the cured product of the photo-curable resin component suppresses the fluidity of the conductive particles at the time of connection, thereby achieving connection. It tends to be excellent in trapping of conductive particles between the electrodes. Further, according to the circuit connection adhesive film 10A, it is possible to reduce the connection resistance of the circuit connection structure.
  • circuit connection adhesive film of the present embodiment has been described above, the present disclosure is not limited to the above embodiment.
  • FIG. 2 is a schematic cross-sectional view showing another embodiment of the circuit-connecting adhesive film, which schematically shows a longitudinal cross-section of the circuit-connecting adhesive film.
  • the circuit-connecting adhesive film may be composed of, for example, two layers of a first adhesive layer and a second adhesive layer. It may be composed of three or more layers including two layers.
  • the circuit-connecting adhesive film is, for example, a third adhesive layer provided on the opposite side of the first adhesive layer to the second adhesive layer, like the circuit-connecting adhesive film 10B shown in FIG.
  • An adhesive layer 5 may be further provided.
  • the third adhesive layer 5 contains at least component (C).
  • the (C1) component and (C2) component used in the (C) component (that is, the third thermosetting resin component) in the third adhesive layer are the (C) component in the first adhesive layer 1 (that is, the first thermosetting resin component), the detailed description is omitted here because it is the same as the components (C1) and (C2) used in the first thermosetting resin component.
  • the third thermoset resin component may be the same as or different from the first thermoset resin component.
  • the third thermoset resin component may be the same as or different from the second thermoset resin component.
  • the content of component (C) is 5% by mass or more, 10% by mass or more, or 15% by mass or more, based on the total mass of the third adhesive layer, from the viewpoint of imparting good transferability and peeling resistance. , or 20% by mass or more.
  • the content of component (C) is 70% by mass or less, based on the total mass of the third adhesive layer, from the viewpoint of imparting good half-cutting properties and anti-blocking properties (suppression of resin exudation from the reel). It may be 60% by mass or less, 50% by mass or less, or 40% by mass or less.
  • the third adhesive layer 5 may further contain other components and other additives in the first adhesive layer 1. Preferred aspects of other components and other additives are the same as those of the first adhesive layer 1 .
  • the content of component (D) may be 10% by mass or more, 20% by mass or more, or 30% by mass or more, and 80% by mass or less, or 70% by mass, based on the total mass of the third adhesive layer. or less, or 60% by mass or less.
  • the content of component (E) may be 0.1 to 10% by mass based on the total mass of the third adhesive layer.
  • the content of component (F) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 50% by mass or less, or 40% by mass, based on the total mass of the third adhesive layer. or less, or 30% by mass or less.
  • the content of other additives may be, for example, 0.1 to 10% by mass based on the total mass of the third adhesive layer.
  • the thickness d3 of the third adhesive layer 5 may be appropriately set according to the height of the electrodes of the circuit members to be adhered.
  • the thickness d3 of the third adhesive layer 5 is 0.2 ⁇ m or more or 0.2 ⁇ m or more from the viewpoint of sufficiently filling the space between the electrodes to seal the electrodes and obtaining better connection reliability. .5 ⁇ m or more, and may be 5.0 ⁇ m or less, or 2.5 ⁇ m or less.
  • the thickness d3 of the third adhesive layer 5 is measured from the surface 5a of the third adhesive layer 5 opposite to the first adhesive layer 1 to the second adhesion It is the distance to the surface 1a on the side opposite to the agent layer 2 side (the distance indicated by d3 in FIG. 2).
  • the thickness d3 of the third adhesive layer 5 can be obtained, for example, in the same manner as the thickness d1 of the first adhesive layer 1 described above.
  • the thickness of the circuit-connecting adhesive film may be the same as the possible thickness range of the circuit-connecting adhesive film 10A.
  • a method for manufacturing an adhesive film for circuit connection of one embodiment comprises a predetermined first adhesive layer and a predetermined second adhesive layer provided on the first adhesive layer.
  • the surface has a plurality of recesses, and each of the plurality of recesses A step of preparing a substrate on which the component (A) is arranged (preparation step), and on the surface of the substrate (the surface on which the recess is formed), the component (B) and the first thermosetting resin component A step of transferring the component (A) to the composition layer (transfer step) by providing a composition layer containing A step of forming a first adhesive layer containing a cured product of and (C) component (first thermosetting resin component) (light irradiation step), and on one side of the first adhesive layer and a step of providing a
  • FIG. 3 is a schematic cross-sectional view of a substrate used for manufacturing the circuit-connecting adhesive film of FIG.
  • FIG. 4 is a diagram showing a state in which conductive particles are arranged in the recesses of the base shown in FIG.
  • FIG. 5 is a schematic cross-sectional view showing one step of the method for producing the circuit-connecting adhesive film of FIG. 1, and is a cross-sectional view schematically showing an example of the transfer step.
  • FIG. 6 is a schematic cross-sectional view showing one step of the method for manufacturing the adhesive film for circuit connection of FIG. 1, and is a cross-sectional view schematically showing an example of the light irradiation step.
  • a substrate 6 having a plurality of recesses 7 on its surface is prepared (see FIG. 3).
  • Base 6 has a plurality of recesses 7 .
  • the plurality of recesses 7 are, for example, regularly arranged in a predetermined pattern (for example, a pattern corresponding to the electrode pattern of the circuit member).
  • the conductive particles 4 are transferred to the composition layer in a predetermined pattern. Therefore, the circuit-connecting adhesive film 10A in which the conductive particles 4 are regularly arranged in a predetermined pattern can also be obtained.
  • the recess 7 of the base 6 is tapered such that the opening area increases from the bottom 7a side of the recess 7 toward the surface 6a of the base 6 . That is, the width of the bottom portion 7a of the recess 7 (width a in FIG. 3) is narrower than the width of the opening of the recess 7 (width b in FIG. 3).
  • the size (width a, width b, volume, taper angle, depth, etc.) of the recesses 7 can be set according to the intended size of the conductive particles and the position of the conductive particles in the circuit-connecting adhesive film. For example, the width (width b) of the opening of the recess 7 may be larger than the maximum particle size of the conductive particles 4 and may be less than twice the maximum particle size of the conductive particles.
  • the shape of the opening of the recess 7 may be circular, elliptical, triangular, quadrangular, polygonal, or the like.
  • the recesses 7 of the substrate 6 can be formed by known methods such as lithography and machining. With these methods, the size and shape of the recess can be freely designed.
  • Materials constituting the base 6 include, for example, inorganic materials such as silicon, various ceramics, glass, metals (stainless steel, etc.), and organic materials such as various resins.
  • the conductive particles 4 can be arranged in the recesses 7 of the substrate 6 by forming the conductive particles 4 in the recesses 7 of the substrate 6.
  • the substrate 6 may be made of a heat-resistant material that does not deteriorate at the melting temperature of the fine particles (for example, solder fine particles) used to form the conductive particles 4 .
  • the conductive particles 4 (component (A) above) are placed (accommodated) in each of the plurality of recesses 7 of the substrate 6 (see FIG. 4).
  • the arrangement method of the conductive particles 4 is not particularly limited.
  • the arrangement method may be either dry or wet.
  • the conductive particles 4 are placed on the surface 6a of the substrate 6, and a squeegee or a slightly adhesive roller is used to rub the surface 6a of the substrate 6, thereby removing the excess conductive particles 4 and filling the concave portions 7 with the conductive particles. 4 can be placed. If the width b of the opening of the recess 7 is greater than the depth of the recess 7 , the conductive particles may fly out of the opening of the recess 7 . By using a squeegee, the conductive particles protruding from the openings of the recesses 7 can be removed.
  • Methods for removing excess conductive particles include, for example, a method of blowing compressed air, a method of rubbing the surface 6a of the substrate 6 with a nonwoven fabric or a bundle of fibers, and the like. These methods are preferable for handling easily deformable particles (for example, solder particles) as conductive particles because the physical force is weaker than that of squeegees. Moreover, in these methods, the conductive particles protruding from the openings of the recesses 7 can be left in the recesses 7 .
  • the conductive particles 4 are solder particles
  • the conductive particles 4 are formed in the recesses 7 of the substrate 6 so that the conductive particles 4 are formed in the recesses. 7 may be placed.
  • fine particles (solder fine particles) for forming the conductive particles 4 are accommodated in the recesses 7 .
  • the conductive particles 4 can be formed in the recesses 7 by melting and fusing the fine particles accommodated in the recesses 7 .
  • the fine particles accommodated in the recesses 7 are united by melting and spheroidized by surface tension. At this time, the molten metal follows the bottom of the recesses 7 at the contact area. . Therefore, for example, when the bottom of the concave portion 7 is flat, the conductive particle 4 has a flat portion 4a on a part of the surface.
  • the substrate 6 After placing the conductive particles 4 in the recesses 7 , the substrate 6 can be handled with the conductive particles 4 placed (accommodated) in the recesses 7 .
  • the conductive particles 4 especially soft conductive particles such as solder particles
  • the conductive particles 4 can be easily taken out. Therefore, it tends to be easy to prevent deformation when the conductive particles 4 are collected and subjected to surface treatment. .
  • the photocurable resin component (component (B) above) and the first thermosetting resin component (component (C) above) are applied onto the surface of the substrate 6 (the surface on which the recesses 7 are formed).
  • the conductive particles 4 are transferred to the composition layer 9 (see FIG. 5).
  • a laminated film 12 is produced by forming a composition layer 9 containing components (B) and (C) on a support 11 .
  • the surface of the substrate 6 on which the recesses 7 are formed (the surface 6a of the substrate 6) and the surface of the laminate film 12 on the composition layer 9 side (the surface 9a of the composition layer 9 on the side opposite to the support 11). are opposed to each other to bring the substrate 6 and the composition layer 9 close to each other (see FIG. 5(a)).
  • the composition layer 9 is brought into contact with the surface 6a of the substrate 6 (the surface where the recesses 7 are formed), and the conductive particles 4 are transferred to the composition layer 9. do.
  • the particle transfer layer 13 including the composition layer 9 and the conductive particles 4 at least partially embedded in the composition layer 9 is obtained (see FIG. 5(b)).
  • the conductive particles 4 have a flat portion 4a corresponding to the shape of the bottom of the concave portion 7, and the flat portion 4a faces the side opposite to the support 11. It is arranged in the composition layer 9 in a state.
  • the composition layer 9 is prepared by dissolving or dispersing components (B) and (C), and other components added as necessary, in an organic solvent by stirring, mixing, kneading, or the like. , a varnish composition (varnish-like first adhesive composition). Specifically, for example, the varnish composition is applied onto the support 11 (for example, a base material subjected to a release treatment) using a knife coater, roll coater, applicator, comma coater, die coater, or the like. Then, the composition layer 9 can be formed by volatilizing the organic solvent by heating. At this time, the thickness of the finally obtained first adhesive layer can be adjusted by adjusting the coating amount of the varnish composition.
  • the organic solvent used in the preparation of the varnish composition is not particularly limited as long as it has the property of uniformly dissolving or dispersing each component.
  • examples of such organic solvents include toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, butyl acetate and the like. These organic solvents can be used individually by 1 type or in combination of 2 or more types.
  • Stirring and mixing or kneading during preparation of the varnish composition can be performed using, for example, a stirrer, a kneader, a three-roll mill, a ball mill, a bead mill, a homodisper, or the like.
  • the support 11 is not particularly limited as long as it has heat resistance that can withstand the heating conditions when volatilizing the organic solvent.
  • the support 11 may be a plastic film or a metal foil.
  • Examples of the support 11 include oriented polypropylene (OPP), polyethylene terephthalate (PET), polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, polyolefin, polyacetate, polycarbonate, polyphenylene sulfide, polyamide, polyimide, cellulose, ethylene/ Substrates (for example, films) made of vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, synthetic rubbers, liquid crystal polymers, and the like are included.
  • OPP oriented polypropylene
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • polyethylene isophthalate polybutylene terephthalate
  • polyolefin polyacetate
  • polycarbonate polypheny
  • the heating conditions for volatilizing the organic solvent from the varnish composition applied to the support 11 can be appropriately set according to the organic solvent used.
  • the heating conditions may be, for example, 40 to 120° C. for 0.1 to 10 minutes.
  • Examples of methods for bonding the laminated film 12 and the substrate 6 include hot pressing, roll lamination, and vacuum lamination. Lamination can be performed, for example, under temperature conditions of 0 to 80°C.
  • the composition layer 9 may be formed by directly applying the varnish composition to the substrate 6, but by using the laminated film 12, the support 11, the composition layer 9 and the conductive particles 4 are integrated. It becomes easy to obtain the particle transfer layer 13 having a high density, and there is a tendency that the light irradiation step to be described later can be easily performed.
  • the composition layer 9 (particle transfer layer 13) is irradiated with light (actinic rays) to cure the component (B) in the composition layer 9 and form the first adhesive layer 1. (see Figure 6).
  • irradiation light containing wavelengths within the range of 150 to 750 nm (eg, ultraviolet light) may be used.
  • Light irradiation can be performed using, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an LED light source, or the like.
  • the integrated amount of light to be irradiated can be appropriately set, and may be, for example, 500 to 3000 mJ/cm 2 .
  • the light is irradiated from the side opposite to the support 11 (the side of the composition layer 9 to which the conductive particles 4 are transferred), but the support 11 receives the light.
  • the light may be irradiated from the support 11 side.
  • the light irradiation is performed after the substrate 6 and the particle transfer layer 13 are separated, but the light irradiation may be performed before the substrate 6 is separated. In this case, light irradiation may be performed after the support 11 is peeled off.
  • the second adhesive layer 2 is provided on the surface of the first adhesive layer 1 opposite to the support 11 (the side of the composition layer 9 to which the conductive particles 4 are transferred). Thereby, the circuit-connecting adhesive film 10A shown in FIG. 1 can be obtained.
  • the second adhesive layer 2 contains, instead of the first adhesive composition, a second thermosetting resin component (component (C) above) and other components added as necessary, organic
  • a method of providing a composition layer 9 on a substrate 6, except for using a varnish composition (second adhesive composition) prepared by dissolving or dispersing by stirring, mixing, kneading, or the like in a solvent. can be provided on the first adhesive layer 1 in the same manner as in . That is, the second adhesive layer is formed on the first adhesive layer 1 by laminating the laminated film obtained by forming the second adhesive layer 2 on the support and the first adhesive layer 1. 2 may be provided, and the second adhesive layer 2 may be provided on the first adhesive layer 1 by directly applying the second adhesive composition to the first adhesive layer 1 .
  • the lamination step by providing the second adhesive layer 2 on the surface opposite to the support 11, the adhesion of the circuit connection adhesive film to the circuit member is improved and the peeling during connection is suppressed. I can expect it.
  • the second adhesive layer 2 may be provided on the surface on which the support 11 was provided. In this case, the lamination step may be performed before the light irradiation step, or may be performed before the transfer step.
  • the method for producing an adhesive film for circuit connection includes providing a third adhesive layer on the surface of the first adhesive layer opposite to the second adhesive layer (second laminating step ) may be further provided.
  • a circuit-connecting adhesive film for example, the circuit-connecting adhesive film 10B shown in FIG. 2 further comprising a third adhesive layer.
  • the third adhesive layer contains, instead of the second adhesive composition, a third thermosetting resin component (component (C) above) and other components added as necessary in an organic solvent.
  • a third thermosetting resin component component (C) above
  • the above laminate for providing the second adhesive layer except for using a varnish composition (third adhesive composition) prepared by dissolving or dispersing by stirring, mixing, kneading, etc. in A third adhesive layer can be provided on the first adhesive layer in the same manner as in the step (first lamination step).
  • the second lamination step may be performed before the first lamination step.
  • circuit connection structure and its manufacturing method a circuit connection structure and its manufacturing method
  • a circuit connection structure and a method for producing the same will be described, taking as an example an aspect in which the circuit connection adhesive film 10A is used as a circuit connection material.
  • FIG. 7 is a schematic cross-sectional view showing one embodiment of the circuit connection structure.
  • the circuit connection structure 100 includes a first circuit board 21 and a first circuit member 23 having a first electrode 22 formed on a main surface 21 a of the first circuit board 21 .
  • a second circuit member 26 having a second circuit board 24 and a second electrode 25 formed on the main surface 24a of the second circuit board 24, and a cured body of the circuit-connecting adhesive film 10A.
  • a circuit connection portion 27 for electrically connecting and bonding the first circuit member 23 and the second circuit member 26 is provided.
  • the first circuit member 23 and the second circuit member 26 may be the same or different.
  • the first circuit member 23 and the second circuit member 26 may be a glass substrate or plastic substrate on which electrodes are formed, a printed wiring board, a ceramic wiring board, a flexible wiring board, an IC chip, or the like.
  • the first circuit board 21 and the second circuit board 24 may be made of an inorganic material such as semiconductor, glass, or ceramic, an organic material such as polyimide or polycarbonate, a composite material such as glass/epoxy, or the like.
  • the first circuit member 23 is a plastic substrate made of an organic substance such as polyimide, polycarbonate, polyethylene terephthalate, cycloolefin polymer, or the like.
  • the second circuit board 24 may be, for example, an IC chip.
  • the first electrode 22 and the second electrode 25 are metals such as gold, silver, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, aluminum, molybdenum, titanium, indium tin oxide (ITO), Electrodes may include oxides such as indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), and the like.
  • the first electrode 22 and the second electrode 25 may be electrodes formed by stacking two or more of these metals, oxides, and the like.
  • the electrode formed by laminating two or more kinds may have two or more layers, or may have three or more layers.
  • the first electrode 22 may be an electrode having a titanium layer on its outermost surface.
  • the first electrode 22 and the second electrode 25 may be circuit electrodes or bump electrodes. At least one of the first electrode 22 and the second electrode 25 may be a bump electrode.
  • the circuit connection structure shown in FIG. 7 is of a mode in which the first electrodes 22 are circuit electrodes and the second electrodes 25 are bump electrodes.
  • the circuit connection portion 27 includes a cured body of the circuit connection adhesive film 10A.
  • the circuit connection portion 27 may be made of a cured body of the circuit connection adhesive film 10A.
  • the circuit connection portion 27 is positioned, for example, on the first circuit member 23 side in the direction in which the first circuit member 23 and the second circuit member 26 face each other (hereinafter, “opposing direction”), and A first cured body region 28 made of a cured body derived from the first adhesive layer of and located on the second circuit member 26 side in the opposite direction and composed of a cured body derived from the second adhesive layer
  • the second cured body region 29 and the conductive particles 4 interposed between at least the first electrode 22 and the second electrode 25 to electrically connect the first electrode 22 and the second electrode 25 to each other have.
  • the circuit connection portion 27 may not have two distinct cured regions, a first cured region 28 and a second cured region 29.
  • a cured body derived from the adhesive layer and a cured body derived from the second adhesive layer may be mixed to form one cured body region.
  • FIG. 8 is a schematic cross-sectional view showing one embodiment of a method for manufacturing a circuit connection structure.
  • 8A and 8B are schematic cross-sectional views showing each step.
  • the first circuit board 21 and the first circuit member 23 including the first electrodes 22 formed on the main surface 21a of the first circuit board 21, and the second circuit board 24 and a second circuit member 26 having a second electrode 25 formed on the main surface 24a of the second circuit board 24 are prepared.
  • the first circuit member 23 and the second circuit member 26 are arranged so that the first electrode 22 and the second electrode 25 face each other, and the first circuit member 23 and the second circuit member 26, the adhesive film 10A for circuit connection is arranged.
  • the circuit connecting adhesive film 10A is placed on the first circuit member 23 so that the first adhesive layer 1 faces the main surface 21a of the first circuit board 21. Laminate on top.
  • the circuit-connecting adhesive film 10A was laminated so that the first electrodes 22 on the first circuit board 21 and the second electrodes 25 on the second circuit board 24 faced each other.
  • a second circuit member 26 is placed on the first circuit member 23 .
  • the conductive particles 4 are fixed in the first adhesive layer 1.
  • the first adhesive layer 1 hardly flows during thermocompression bonding and the conductive particles are efficiently captured between the facing electrodes, the first electrode 22 and the second electrode facing each other 25 is reduced.
  • the thickness of the first adhesive layer is 5.0 ⁇ m or less, and the ratio of the thickness of the first adhesive layer to the average particle size of the conductive particles is 0.50 or more. It is possible to suppress the increase in the connection resistance between the opposing circuits by reducing the amount of resin between them.
  • the heating temperature for thermocompression bonding can be set as appropriate, and may be, for example, 50 to 190°C. Pressurization is not particularly limited as long as it does not damage the adherend.
  • the area conversion pressure at the bump electrode may be 10 to 50 MPa, and may be 0.1 to 40 MPa.
  • the area-converted pressure at the bump electrode may be 10 to 100 MPa.
  • the following materials were used as the (B1) component, (B2) component, (b2) component, (C1) component, (C2) component, (D) component, (E) component, and ( F) Used as a component.
  • Thermoplastic resin D-1 Phenotote FX-293 (phenoxy resin, manufactured by Nippon Steel Chemical & Materials Co., Ltd.)
  • Thermoplastic resin D-2 Phenotote ZX-1356-2 (phenoxy resin, manufactured by Nippon Steel Chemical & Materials Co., Ltd.)
  • Thermoplastic resin D-3 Phenotote YP-70 (phenoxy resin, manufactured by Nippon Steel Chemical & Materials Co., Ltd.)
  • Coupling agent E-1 SH-6040 (3-glycidoxypropyltrimethoxysilane, manufactured by Dow Corning Toray Co., Ltd.)
  • F Component: Filler Filler F-1: ADMAFINE SE2050 (silica fine particles, manufactured by Admatechs Co., Ltd.) Filler F-2: Aerosil R805 (silica fine particles, manufactured by Evonik Industries AG)
  • the concave portion has a truncated cone shape with an opening area that expands toward the surface of the base (the center of the bottom and the center of the opening are the same when viewed from the top of the opening), and the diameter of the opening is 4.3 ⁇ m ⁇ and the diameter of the bottom is 4. 0 ⁇ m ⁇ , depth: 4.0 ⁇ m.
  • the plurality of recesses were regularly formed in a three-sided arrangement at intervals of 8.0 ⁇ m (center-to-center distance between the bottoms) so that the density of the conductive particles was 18,000 per 1 mm 2 (18,000/mm 2 ). .
  • conductive particles A-1 (average particle size: 3.2 ⁇ m) are obtained by Ni-plating the surface of the plastic core and displacing the outermost surface with Pd. ) was prepared and placed on the surface of the base on which the recesses were formed. Then, the surface of the substrate on which the recesses are formed was rubbed with a slightly adhesive roller to remove excess conductive particles, which were placed only in the recesses. The amount of the conductive particles A-1 in the recesses was adjusted as shown in Table 1 (unit: parts by mass).
  • the average particle diameter of the conductive particles A-1 is obtained by cutting the first adhesive layer prepared through the steps (b) and (c) described later into 10 cm ⁇ 10 cm, and on the surface on which the conductive particles are arranged. It is a value measured by SEM observation of 300 conductive particles after Pt sputtering.
  • the (B1) component, (B2) component, (C1) component, (C2) component, (D) component, and (E) component shown in Table 1 are was mixed with an organic solvent (2-butanone) at a compounding amount (unit: parts by mass, solid content) shown in , to obtain a varnish-like first adhesive composition.
  • the first adhesive composition was applied to a PET film having a thickness of 38 ⁇ m that had been subjected to a silicone release treatment, and dried with hot air at 60° C. for 3 minutes to form a composition layer having a thickness of 3.0 ⁇ m on the PET film. was made.
  • Step (b2) transfer of conductive particles
  • ⁇ Step (d1): Preparation of second adhesive layer Component (C1), component (C2), component (D), component (E), and component (F) shown in Table 2 are blended as shown in Table 2.
  • a varnish-like second adhesive composition was obtained by mixing with an organic solvent (2-butanone) in an amount (unit: parts by mass, solid content).
  • the second adhesive composition is applied to a PET film having a thickness of 50 ⁇ m that has been subjected to a silicone release treatment, and dried with hot air at 60° C. for 3 minutes to form a second adhesive layer 2A on the PET film. bottom.
  • the first adhesive layer 1A produced in the step (c) and the second adhesive layer 2A produced in the step (d1) were heated at 50°C. They were laminated while applying heat. As a result, a two-layer circuit connection adhesive film with a PET film was obtained.
  • the blending amounts shown in Table 3 of the components (C1), (C2), (D), (E) and (F) shown in Table 3 (Unit: parts by mass, solid content) was mixed with an organic solvent (2-butanone) to obtain a varnish-like third adhesive composition.
  • the third adhesive composition is applied to a PET film having a thickness of 50 ⁇ m that has been subjected to a silicone release treatment, and dried with hot air at 60° C. for 3 minutes to form a third adhesive layer 3A on the PET film. bottom.
  • Step (e2) Lamination of third adhesive layer Exposed by peeling off the PET film on the first adhesive layer 1A side of the two-layer circuit connection adhesive film produced in step (d2)
  • the first adhesive layer 1A and the third adhesive layer 3A prepared in the step (e1) were laminated while applying a temperature of 50°C.
  • an adhesive film for circuit connection having a three-layer structure of Example 1 was obtained.
  • the flow ratio of the first adhesive layer to the second adhesive layer was calculated by the following method using the two-layer circuit connection adhesive film with the PET film produced in step (d2).
  • cover glass manufactured by Matsunami Glass Industry Co., Ltd. (thickness 0.15 mm, width 18 mm, depth 18 mm), and using a thermocompression device LD-06 manufactured by Ohashi Seisakusho Co., Ltd. under the conditions of a crimping temperature of 60 ° C., a crimping pressure of 10 MPa, and a crimping time of 0.1 second.
  • a temporary fixed body (cover glass/adhesive film for evaluation/PET film) was obtained by thermocompression bonding from the adhesive layer side.
  • the pressure bonding temperature is the temperature reached when pressure bonding is performed for 1 second
  • the pressure bonding pressure is the area-converted pressure of the adhesive film for evaluation.
  • a cover glass (thickness 0.15 mm, width 18 mm, depth) manufactured by Matsunami Glass Industry Co., Ltd. is placed on the second adhesive layer. 18 mm) was placed to obtain a laminate (cover glass/adhesive film for evaluation/cover glass). Then, using a thermocompression bonding apparatus BD-06 manufactured by Ohashi Seisakusho Co., Ltd., the laminate is thermocompression bonded from the second adhesive layer side under the conditions of a compression temperature of 170 ° C., a compression pressure of 60 MPa, and a compression time of 5 seconds.
  • the compression temperature is the maximum temperature reached by the adhesive film for evaluation
  • the compression pressure is the area-converted pressure of the adhesive film for evaluation.
  • a dummy sample (the same laminate as the laminate for evaluation) was separately prepared to determine the maximum temperature reached, and a thin temperature sensor (Rika Thermo-compression bonding was performed with ST-50 (manufactured by Kogyo Co., Ltd.) sandwiched between them, and the maximum temperature reached by the adhesive film in the dummy sample was measured in advance and adjusted.
  • the pressed body is observed with an optical microscope (L300ND manufactured by Nikon Corporation), and a length measuring tool is used to measure the adhesive area S1 (unit: mm 2 ), and the adhesion area S2 (unit: mm 2 ) between the second adhesive layer and the glass plate after curing, and based on the following formula (a), the second adhesive layer for the second adhesive layer
  • the thicknesses of the first adhesive layer, the second adhesive layer, and the third adhesive layer were measured.
  • the adhesive film for circuit connection was sandwiched between two sheets of glass (thickness: about 1 mm), and 100 g of bisphenol A type epoxy resin (trade name: JER811, manufactured by Mitsubishi Chemical Corporation) and a curing agent (trade name: Epomount curing agent, manufactured by Refinetech Co., Ltd.) 10 g of the resin composition is cast, the cross section is polished using a polishing machine, and a scanning electron microscope (SEM, trade name: SE-8020, Hitachi, Ltd.) is used. Hitech Science) was used to measure the thickness of the first adhesive layer, the second adhesive layer, and the third adhesive layer.
  • the first adhesive layer, second adhesive layer, and third adhesive layer were 3.0 ⁇ m, 9.0 ⁇ m, and 1.0 ⁇ m, respectively
  • Examples 2 to 5 and Comparative Examples 1 and 2 A varnish-like first adhesive composition was prepared in the same manner as in Example 1, except that in step (b1), the types and/or amounts of the materials to be blended were changed as shown in Table 4. to prepare the first adhesive layers 1B to 1G. Subsequently, in the same manner as in Example 1, a second adhesive layer 2A and a third adhesive layer 3A were laminated on the first adhesive layers 1B to 1G, respectively, and Examples 2 to 5 and Comparative Example An adhesive film for circuit connection having a three-layer configuration of 1 and 2 was produced. Comparative Example 2 is an adhesive film for circuit connection that does not contain a radically polymerizable compound.
  • a photocationic polymerization initiator (photooxygen generator) was used as the following component (c2).
  • the thickness of each adhesive layer, the flow ratio, the conductive particle density, and the monodispersity of the conductive particles were determined in the same manner as in Example 1. asked for Table 5 shows the results.
  • ⁇ (c2) component photocationic polymerization initiator photocationic polymerization initiator c2-1: CPI-310B (triarylsulfonium salt, manufactured by San-Apro Co., Ltd.)
  • circuit connection structure (Preparation of circuit connection structure) Using the adhesive films for circuit connection of Examples 1 to 5 and Comparative Examples 1 and 2, circuit connection structures were produced. A width of 2.0 mm was cut from the circuit-connecting adhesive film, and the circuit-connecting adhesive film was placed on the first circuit member so that the first adhesive layer and the first circuit member were in contact with each other. Using a thermal temporary pressure bonding device (LD-06, manufactured by Ohashi Seisakusho Co., Ltd.) consisting of a stage made of a ceramic heater and a tool (8 mm ⁇ 50 mm), conditions of 70 ° C.
  • LD-06 thermal temporary pressure bonding device
  • the manufactured circuit connection structure was observed from the Al-coated glass substrate using a differential interference microscope (trade name: L300ND, manufactured by Nikon Corporation), and the number of conductive particles present per gold bump was measured. , the average value of which was calculated.
  • the number of conductive particles present on the gold bump was measured at 100 points, and the average value of these 100 points was defined as the number of captured conductive particles, and evaluated according to the following criteria. Table 5 shows the results. It can be said that the larger the number of trapped conductive particles, the better the conduction characteristics are ensured between the opposing electrodes.
  • B Less than 5
  • connection resistance (Preparation of circuit connection structure) Using the adhesive films for circuit connection of Examples 1 to 5 and Comparative Examples 1 and 2, circuit connection structures were produced. A plastic substrate with a Ti/Al/Ti circuit (thickness: 0.05 mm) was used as the first circuit member. A circuit connection structure was produced in the same manner as in [Evaluation of conductive particle trapping property] except that it was changed to .
  • connection resistance The initial connection resistance (conduction resistance) of the produced circuit connection structure was measured by the four-probe method. For the measurement, using a constant current power supply R-6145 manufactured by Advantest Co., Ltd., a constant current (1 mA) is applied between the circuit electrode of the first circuit member of the circuit connection structure and the circuit electrode of the second circuit member ( connection). The potential difference at the connecting portion when the current was applied was measured using a digital multimeter (R-6557) manufactured by ADVANTEST CORPORATION. The potential difference was measured at arbitrary 14 points, and the average value was obtained. Table 5 shows the results. It can be said that the smaller the connection resistance value is, the better the conduction characteristics are ensured between the opposing electrodes. A: Less than 1.2 ⁇ B: 1.2 or more and less than 1.5 ⁇ C: 1.5 ⁇ or more and less than 2.0 ⁇ D: 2.0 ⁇ or more
  • the circuit connecting adhesive films of Examples 1-5 having a flow ratio of the first adhesive layer to the second adhesive layer of 0.30 to 0.80 were able to trap conductive particles. It was excellent in terms of both toughness and connection resistance.
  • the adhesive film for circuit connection of Comparative Example 1 in which the flow ratio of the first adhesive layer to the second adhesive layer exceeds 0.80, does not have sufficient scavenging properties for the conductive particles.
  • SYMBOLS 1 First adhesive layer, 2... Second adhesive layer, 3... Adhesive component, 4... Conductive particles, 5... Third adhesive layer, 6... Substrate, 7... Recess, 9... Composition Layers 10A, 10B... Adhesive film for circuit connection 21... First circuit board 22... First electrode (circuit electrode) 23... First circuit member 24... Second circuit board 25... Second electrode (bump electrode) 26 Second circuit member 27 Circuit connection part 100 Circuit connection structure.

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