WO2022107800A1 - 回路接続用接着剤フィルム、並びに、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、接続構造体及びその製造方法 Download PDF

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Publication number
WO2022107800A1
WO2022107800A1 PCT/JP2021/042211 JP2021042211W WO2022107800A1 WO 2022107800 A1 WO2022107800 A1 WO 2022107800A1 JP 2021042211 W JP2021042211 W JP 2021042211W WO 2022107800 A1 WO2022107800 A1 WO 2022107800A1
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WO
WIPO (PCT)
Prior art keywords
electrode
solder particles
adhesive film
circuit
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2021/042211
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English (en)
French (fr)
Japanese (ja)
Inventor
敏光 森谷
邦彦 赤井
勝将 宮地
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
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Showa Denko Materials Co Ltd
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Priority to KR1020237019088A priority Critical patent/KR20230109659A/ko
Priority to CN202180077955.5A priority patent/CN116529838A/zh
Priority to JP2022563795A priority patent/JP7798036B2/ja
Publication of WO2022107800A1 publication Critical patent/WO2022107800A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • 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

Definitions

  • the present invention relates to an adhesive film for circuit connection, a connection structure, and a method for manufacturing the same.
  • the method of mounting a liquid crystal drive IC on a liquid crystal display glass panel can be roughly divided into two types: COG (Chip-on-Glass) mounting and COF (Chip-on-Flex) mounting.
  • COG mounting for example, a liquid crystal drive IC is directly bonded onto a glass panel using a film-shaped circuit connection adhesive (hereinafter referred to as “circuit connection adhesive film”).
  • circuit connection adhesive film film-shaped circuit connection adhesive
  • COF mounting for example, a liquid crystal driving IC is bonded to a flexible tape having metal wiring, and they are bonded to a glass panel using an adhesive film for circuit connection.
  • the metal bumps which are the circuit electrodes of liquid crystal drive ICs, have become narrower in pitch and area. Therefore, conductive particles in the adhesive may flow out between adjacent circuit electrodes to cause a short circuit. This tendency is particularly remarkable in COG mounting.
  • the number of conductive particles captured between the metal bump and the glass panel decreases, and the connection resistance between the opposing circuit electrodes increases, which may lead to poor connection. be.
  • Patent Document 1 proposes a method of adhering spherical resin particles to the surface of conductive particles.
  • the present invention is an adhesive for circuit connection, which can secure sufficient insulation between adjacent electrodes while ensuring a sufficient capture rate of conductive particles without using the above-mentioned insulating coated conductive particles.
  • the main purpose is to provide the film.
  • One aspect of the present invention relates to the circuit connection adhesive film shown in [1] below.
  • thermosetting adhesive film for circuit connection having an average particle size of 1 to 30 ⁇ m, and having a particle size of C.I. V.
  • the ratio of the thickness of the adhesive film for circuit connection to the average particle diameter of the solder particles containing the solder particles having a value of 20% or less is more than 1.0 and less than 1.5, and the solder particles have a value of more than 1.0.
  • An adhesive film for circuit connection, where the melting point is T m ° C., the curing rate at T m ° C. when heated at a heating rate of 10 ° C./min under a nitrogen atmosphere is 80% or more.
  • the adhesive film for circuit connection on the above side surface, it is possible to secure sufficient insulation between adjacent electrodes while ensuring a sufficient capture rate of conductive particles (solder particles).
  • the "capture rate” means the ratio of the number of conductive particles captured per unit area of the connection point to the number of conductive particles (solder particles) per unit area of the adhesive film for circuit connection. ..
  • a circuit member having a low electrode height has come to be used.
  • the total height of the electrodes to be connected may be smaller than the particle diameter of the conductive particles used in the circuit connection adhesive.
  • a circuit connection adhesive containing the above-mentioned insulating coated conductive particles for example, a circuit connection adhesive
  • the circuit connection adhesive film on the side surface even when the total height of the connected electrodes is smaller than the particle size of the conductive particles, the conductive particles (solder particles) are sufficiently captured. Sufficient insulation between adjacent electrodes can be ensured while ensuring the ratio.
  • the circuit connection adhesive film on the side surface may be the circuit connection adhesive film shown in the following [2] to [6].
  • Another aspect of the present invention relates to the connection structure shown in [7] below.
  • the electrodes are provided with a connecting portion for electrically connecting the electrodes of the above to each other via a solder layer and for adhering the first circuit member and the second circuit member, and the connecting portions are [1] to [ A connection structure comprising a cured product of the adhesive film for circuit connection according to any one of 6].
  • connection structure on the side surface may be the connection structure shown in [8] below.
  • Another aspect of the present invention relates to a method for manufacturing a connection structure shown in the following [9].
  • the surface of the first circuit member having the first electrode on which the first electrode is provided and the second electrode of the second circuit member having the second electrode are provided.
  • the circuit connection adhesive film according to [1] to [6] is arranged between the surfaces, and the first circuit member, the circuit connection adhesive film, and the second circuit member
  • the method for manufacturing the connection structure on the above side surface may be the method shown in the following [10].
  • an adhesive film for circuit connection which can secure sufficient insulation between adjacent electrodes while ensuring a sufficient capture rate of conductive particles (solder particles). ..
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of an adhesive film for circuit connection.
  • FIG. 2 is a schematic plan view showing an example of arrangement of conductive particles in the circuit connection adhesive film of FIG. 1.
  • FIG. 3 is a schematic plan view showing an example of arrangement of conductive particles in the circuit connection adhesive film of FIG.
  • FIG. 4 is a schematic cross-sectional view of a substrate used for manufacturing the circuit connection adhesive film of FIG.
  • FIG. 5 is a diagram showing a modified example of the cross-sectional shape of the recess of the substrate of FIG.
  • FIG. 6 is a diagram showing a state in which solder particles are arranged in the recesses of the substrate of FIG.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of an adhesive film for circuit connection.
  • FIG. 2 is a schematic plan view showing an example of arrangement of conductive particles in the circuit connection adhesive film of FIG. 1.
  • FIG. 3 is a schematic plan view showing an example of arrangement of conductive particles in the circuit connection
  • FIG. 7 is a schematic cross-sectional view showing one step of the method for manufacturing the adhesive film for circuit connection of FIG.
  • FIG. 8 is a schematic cross-sectional view showing one step of the method for manufacturing the adhesive film for circuit connection of FIG.
  • FIG. 9 is a schematic cross-sectional view showing an embodiment of the connection structure.
  • FIG. 10 is a schematic cross-sectional view showing an embodiment of a method for manufacturing a connection structure.
  • each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the term "(meth) acrylate” means at least one of an acrylate and a corresponding methacrylate. The same applies to other similar expressions such as "(meth) acryloyl”.
  • the circuit connection adhesive film of one embodiment is a thermosetting adhesive film, and has an average particle diameter of 1 to 30 ⁇ m as conductive particles, and has a particle diameter of C.I. V. Contains solder particles with a value of 20% or less.
  • for circuit connection means that it is used for connection of circuit members (for example, mounting of a light emitting element).
  • the adhesive film for circuit connection may or may not have anisotropic conductivity. That is, the adhesive film for circuit connection may be an anisotropically conductive adhesive film or a non-anisotropically conductive (for example, isotropically conductive) adhesive film.
  • anisotropic conductivity means that the material conducts in the pressurized direction and maintains the insulating property in the non-pressurized direction.
  • circuit connection adhesive film of one embodiment will be described with reference to FIG. 1.
  • FIG. 1 is a diagram schematically showing a vertical cross section of an adhesive film for circuit connection according to an embodiment.
  • the "longitudinal cross section” means a cross section (cross section in the thickness direction) substantially orthogonal to the main surface of the adhesive film for circuit connection.
  • the circuit connection adhesive film 10 shown in FIG. 1 is composed of a thermosetting adhesive film 1 and solder particles 2 arranged in the adhesive film 1.
  • the adhesive film 1 includes a first adhesive layer 3 and a second adhesive layer 4 provided on the first adhesive layer 3.
  • the first adhesive layer 3 is a layer on which the solder particles 2 are transferred in the method for manufacturing the circuit connection adhesive film 10 described later.
  • the solder particles 2 are arranged in the vicinity of the boundary S between the first adhesive layer 3 and the second adhesive layer 4, and the boundary S is located at a separated portion between the adjacent solder particles 2 and 2. ..
  • the surface of the solder particles 2 (the surface on the side of the second adhesive layer 4) is exposed from the surface of the first adhesive layer 3, but the entire solder particles 2 are the first. It may be embedded in the adhesive layer 3.
  • the "horizontal direction” means a direction substantially parallel to the main surface of the circuit connection adhesive film (horizontal direction in FIG. 1). It can be confirmed that the adjacent solder particles are arranged in the horizontal direction in a state of being separated from each other by observing the vertical cross section of the adhesive film for circuit connection with, for example, a scanning electron microscope or the like.
  • the shortest distance (d11 and d21 in FIG. 1) to the surface 4a) opposite to the adhesive layer 3 side may be 0.05 to 1.5 ⁇ m.
  • the adhesive resin can be satisfactorily filled between the circuit members after crimping, so that the insulating property of the circuit tends to be improved, and the shortest distances d11 and d21 are 1.
  • the shortest distances d11 and d21 may be 0.1 ⁇ m or more or 0.2 ⁇ m or more, and may be 1.4 ⁇ m or less or 1.2 ⁇ m or less.
  • the shortest distance d11 and the shortest distance d21 may be the same or different.
  • FIGS. 2 and 3 are plan views schematically showing an arrangement example of the solder particles 2 in the circuit connection adhesive film 10.
  • the solder particles 2 may be arranged in a predetermined pattern in a plan view of the circuit connection adhesive film.
  • the solder particles 2 are arranged at regular and substantially even intervals with respect to the entire region of the circuit connection adhesive film 10, but as shown in FIG. 3, for example, circuit connection adhesion.
  • the solder particles 2 are regularly formed so that the region 10d in which the plurality of solder particles 2 are regularly arranged and the region 10e in which the solder particles 2 do not substantially exist are regularly formed. It may be arranged.
  • the position and number of the solder particles 2 can be set, for example, according to the shape, size, pattern, and the like of the electrodes to be connected.
  • the fact that at least a part of the plurality of solder particles is lined up in a predetermined pattern means that the circuit connection adhesive film is observed from above the main surface of the circuit connection adhesive film using, for example, an electron microscope. Can be confirmed by.
  • the ratio (single dispersion ratio) in which the solder particles 2 exist in a state of being separated from the other solder particles 2 is preferably 90.0% or more, 93.0% or more, and 95.0. % Or more, 97.0% or more, or 98.0% or more.
  • the upper limit of the simple dispersion rate is 100%. The higher the monodispersity, the easier it is to obtain a connection structure with excellent insulation reliability.
  • Such a dispersed state can be formed by using a substrate in which the solder particles 2 are arranged in a predetermined arrangement in the method for manufacturing the adhesive film 10 for circuit connection described later.
  • the circuit connection adhesive film 10 has a thickness larger than 1.0 times and less than 1.5 times the average particle diameter of the solder particles 2. That is, the ratio of the thickness of the circuit connecting adhesive film 10 to the average particle diameter of the solder particles 2 is more than 1.0 and less than 1.5.
  • the ratio of the thickness of the adhesive film 10 for circuit connection to the average particle diameter of the solder particles 2 further improves the capture rate of the solder particles 2 between the opposing electrodes and further improves the insulation resistance between the adjacent electrodes. From the viewpoint, it may be 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less.
  • the ratio of the thickness of the circuit connection adhesive film 10 to the average particle diameter of the solder particles 2 is 1.0 or more and 1.4 or less, 1.0 or more and 1.3 or less, and 1.0 or more and 1.2 or less. Or it may be more than 1.0 and 1.1 or less.
  • the thickness of the circuit connection adhesive film 10 is equal to the thickness of the adhesive film 1.
  • the thickness of the circuit connection adhesive film 10 may be, for example, 2.0 ⁇ m or more, 3.0 ⁇ m or more, or 4.0 ⁇ m or more, and may be 10.0 ⁇ m or less, 8.0 ⁇ m or less, or 6.0 ⁇ m or less. It may be 2.0 to 10.0 ⁇ m, 3.0 to 8.0 ⁇ m or 4.0 to 6.0 ⁇ m.
  • the circuit connection adhesive film 10 has a curing rate of 80% or more at T m ° C. when heated at a heating rate of 10 ° C./min under a nitrogen atmosphere. ..
  • the melting point of the solder particles is usually lower than the curing temperature of the adhesive component.
  • the thickness of the circuit connection adhesive film 10 is less than 1.5 times the average particle size of the conductive particles, the amount of the adhesive component is smaller than the amount of the conductive particles, so that the solder is used as the conductive particles.
  • the insulating property may be deteriorated (for example, short circuit is likely to occur) due to the solder diffused in the adhesive film 1 by thermocompression bonding at the time of connection.
  • the adhesive film 1 is cured before the solder particles 2 are melted by thermocompression bonding at the time of connection, and the diffusion of the solder is suppressed. Even if the thickness of the adhesive film 10 for soldering is less than 1.5 times the average particle size of the conductive particles, sufficient insulation between adjacent electrodes is ensured.
  • the curing rate at Tm ° C. under the above conditions may be 85% or more, 90% or more, or 95% or more, and may be 100%, from the viewpoint of improving the insulating property between adjacent electrodes. May be good.
  • the curing rate of the adhesive film 10 for circuit connection (curing rate at Tm ° C. when heated at a heating rate of 10 ° C./min under a nitrogen atmosphere) is determined by using a differential scanning calorimeter. It can be obtained by using the calorific value measured in the above. Specifically, using a differential scanning calorimeter, the calorific value of the adhesive film 10 for circuit connection is measured at a temperature rise rate of 10 ° C./min under a nitrogen (N 2 ) atmosphere, and the heat generation amount is measured from 50 ° C. for circuit connection. After determining the calorific value (Q 1 ) until the adhesive film 10 is completely cured and the calorific value (Q 2 ) from 50 ° C. to the melting point Tm ° C.
  • the calculated values are calculated by the following formula (Q 2).
  • the curing rate can be calculated by substituting into A).
  • the circuit connection adhesive film 10 is complete when the rate of change of the differential curve (DDSC curve) of the DSC curve obtained by measurement is 0.01 [W ⁇ g ° C] or less. It is judged that it has hardened.
  • Curing rate (%) Q 2 / Q 1 x 100 (A)
  • the circuit connection adhesive film 10 having the above-mentioned curing rate can be prepared by those skilled in the art, for example, by using a compound having a cyclic ether group or the like as a thermosetting component, selecting the type of polymerization initiator, adjusting the blending amount, and the like. If there is, it can be easily produced.
  • the circuit connection adhesive film 10 having the above-mentioned characteristics adheres the first circuit member having the first electrode and the second circuit member having the second electrode, and also adheres the first electrode and the second. It is suitably used for applications in which the electrodes of the above are electrically connected to each other.
  • the circuit connection adhesive film 10 contains solder particles as conductive particles, and the thickness is larger than 1.0 times and less than 1.5 times the average particle diameter of the solder particles 2. It is suitably used for mounting at a low pressure (for example, 5 MPa or less based on the area of the circuit member having the smaller adhesive area among the first circuit member or the second circuit member).
  • the circuit connection adhesive film 10 it is possible to secure sufficient insulation between adjacent electrodes while ensuring a sufficient capture rate of conductive particles (solder particles).
  • the above effect is remarkable when the total height of the connected electrodes (the total height of the first electrode and the height of the second electrode) is smaller than the average particle diameter of the solder particles. Become. Further, according to the circuit connection adhesive film 10, there is a tendency to obtain a sufficiently low connection resistance.
  • the adhesive film 1 is, for example, an insulating adhesive film made of a non-conductive material (insulating resin or the like).
  • the first adhesive layer 3 and the second adhesive layer 4 constituting the adhesive film 1 are each composed of a thermosetting adhesive composition.
  • the adhesive composition constituting the first adhesive layer 3 may be referred to as a “first adhesive composition”
  • the adhesive composition constituting the second adhesive layer 4 may be referred to as a “first adhesive composition”. 2 adhesive composition ".
  • the adhesive composition (first adhesive composition and second adhesive composition) contains at least a thermosetting component.
  • Thermosetting components are components that are fluid at the time of connection and are cured by heating.
  • the adhesive composition may contain a polymerizable compound and a thermal polymerization initiator as the thermosetting component.
  • the polymerizable compound may be a cationically polymerizable compound
  • the thermal polymerization initiator may be a thermal cationic polymerization initiator.
  • the cationically polymerizable compound may be a compound having a cyclic ether group from the viewpoint of further improving the effect of reducing the connection resistance and improving the connection reliability.
  • the compounds having a cyclic ether group when at least one selected from the group consisting of an alicyclic epoxy compound and an oxetane compound is used, the effect of reducing the connection resistance tends to be further improved.
  • the cationically polymerizable compound may contain both an alicyclic epoxy compound and an oxetane compound from the viewpoint that the desired melt viscosity can be easily obtained.
  • the alicyclic epoxy compound can be used without particular limitation as long as it is a compound having an alicyclic epoxy group (for example, an epoxycyclohexyl group).
  • Commercially available alicyclic epoxy compounds include seroxide 8010 (trade name, B-7-oxavicyclo [4.1.0] heptane, manufactured by Daicel Corporation), for example, EHPE3150, EHPE3150CE, seroxide 2021P, and seroxide. 2081 (trade name, manufactured by Daicel Corporation) and the like can be mentioned. These may use one kind of compound alone or may use a plurality of kinds in combination.
  • the oxetane compound can be used without particular limitation as long as it is a compound having an oxetaneyl group.
  • examples of commercially available oxetane compounds include ETERNACOLL OXBP (trade name, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, manufactured by Ube Kosan Co., Ltd.), OXSQ, OXT-121, and the like. Examples thereof include OXT-221, OXT-101, and OXT-212 (trade name, manufactured by Toa Synthetic Co., Ltd.). These may use one kind of compound alone or may use a plurality of kinds in combination.
  • an epoxy compound other than the alicyclic epoxy compound may be used.
  • an epoxy compound having an aromatic hydrocarbon group such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin (for example, a trade name "jER1010" manufactured by Mitsubishi Chemical Corporation) may be used.
  • the epoxy compound having an aromatic hydrocarbon group may be used in combination with the alicyclic epoxy compound from the viewpoint of further improving the effect of reducing the connection resistance and improving the connection reliability.
  • the thermal cationic polymerization initiator is, for example, a compound (thermal latent cation generator) capable of generating an acid or the like by heating to initiate polymerization.
  • the thermal cationic polymerization initiator may be a salt compound composed of a cation and an anion.
  • Thermal cationic polymerization initiators are, for example, BF 4- , BR 4- ( R indicates a phenyl group substituted with two or more fluorine atoms or two or more trifluoromethyl groups), PF 6- , SbF 6 - , AsF 6- , and the like, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, iodonium salts, anilinium salts, onium salts such as pyridinium salts, and the like, which have anions such as. These may be used individually by 1 type, or may be used in combination of a plurality of types.
  • the thermal cationic polymerization initiator may be, for example, a salt compound having an anion containing boron as a constituent element.
  • a salt compound include salt compounds having BF 4- or BR 4- ( R indicates a phenyl group substituted with two or more fluorine atoms or two or more trifluoromethyl groups). Be done.
  • the anion containing boron as a constituent element may be BR 4- , and more specifically, tetrakis (pentafluorophenyl) borate.
  • the thermal cation polymerization initiator may be a salt compound having a cation represented by the following formula (I) or the following formula (II) from the viewpoint of storage stability.
  • R 1 and R 2 each independently represent an organic group containing a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having or not substituted.
  • R 3 represent an alkyl group having 1 to 6 carbon atoms.
  • the salt compound having a cation represented by the formula (I) may be an aromatic sulfonium salt compound (aromatic sulfonium salt type thermoacid generator) from the viewpoint of achieving both storage stability and low temperature activity. That is, at least one of R 1 and R 2 in the formula (I) may be an organic group having a substituent or containing an unsubstituted aromatic hydrocarbon group.
  • the anion in the salt compound having a cation represented by the formula (I) may be an anion containing antimony as a constituent element, and may be, for example, hexafluoroantimonate (hexafluoroantimonic acid).
  • Specific examples of the compound having a cation represented by the formula (I) include 1-naphthylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Co., Ltd., SI-60 main agent).
  • R 4 and R 5 each independently represent an organic group containing a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having or not substituted.
  • R 6 and R 7 each independently represent an alkyl group having 1 to 6 carbon atoms.
  • the salt compound having a cation represented by the formula (II) is, for example, an anilinium salt compound because it has resistance to a substance that can cause curing inhibition to cation curing. It's okay. That is, at least one of R 4 and R 5 in the formula (II) may be an organic group having a substituent or containing an unsubstituted aromatic hydrocarbon group.
  • the anilinium salt compound include N, N-dialkylanilinium salts such as N, N-dimethylanilinium salt and N, N-diethylanilinium salt.
  • the anion in the salt compound having a cation represented by the formula (II) may be an anion containing boron as a constituent element, and may be, for example, tetrakis (pentafluorophenyl) borate.
  • the compound having a cation represented by the formula (II) may be an anilinium salt having an anion containing boron as a constituent element.
  • anilinium salt compounds include CXC-1821 (trade name, manufactured by King Industries) and the like.
  • the content of the thermally cationic polymerization initiator is, for example, 0.1 to 20 parts by mass and 1 to 18 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound from the viewpoint of ensuring the formability and curability of the adhesive film. It may be 3 to 15 parts by mass or 5 to 12 parts by mass.
  • the content of the thermal cationic polymerization initiator in the first adhesive composition (based on 100 parts by mass of the cationically polymerizable compound in the first adhesive composition) may be in the above range, and the second adhesion may occur.
  • the content of the thermally cationic polymerization initiator in the agent composition (based on 100 parts by mass of the cationically polymerizable compound in the second adhesive composition) may be in the above range.
  • the content of the heat-curable component (for example, the total content of the polymerizable compound and the heat polymerization initiator) is, for example, 5 based on the total mass of the adhesive composition from the viewpoint of ensuring the curability of the adhesive film. It may be 1% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more.
  • the content of the thermosetting component is, for example, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 40, based on the total mass of the adhesive composition, from the viewpoint of ensuring the formability of the adhesive film. It may be mass% or less.
  • the content of the thermosetting component is, for example, 5 to 70% by mass, 10 to 60% by mass, 15 to 50% by mass or 20 to 40% by mass, based on the total mass of the adhesive composition. May be.
  • the content of the thermosetting component in the first adhesive composition (based on the total mass of the first adhesive composition) may be in the above range, and the thermosetting component in the second adhesive composition may be thermally cured.
  • the content of the sex component (based on the total mass of the second adhesive composition) may be in the above range.
  • the content of each component contained in the adhesive composition is the content of the thermosetting component in the first adhesive composition (first adhesive). It can be paraphrased as the content of the thermosetting component in the second adhesive composition (based on the total mass of the second adhesive composition).
  • the adhesive composition may further contain, for example, a thermoplastic resin, a filler, a coupling agent, or the like, in addition to the thermosetting component.
  • thermoplastic resin contributes to the improvement of the film formability of the adhesive film.
  • thermoplastic resin include phenoxy resin, polyester resin, polyamide resin, polyurethane resin, polyester urethane resin, acrylic rubber, epoxy resin (solid at 25 ° C.) and the like.
  • phenoxy resin include a fluorene type phenoxy resin, a bisphenol A / bisphenol F copolymer type phenoxy resin, and the like. These may be used individually by 1 type, or may be used in combination of a plurality of types.
  • the weight average molecular weight (Mw) of the thermoplastic resin may be, for example, 5000 to 200,000, 10000 to 100,000, 20000 to 80000 or 40,000 to 60000 from the viewpoint of resin exclusion during mounting.
  • Mw means a value measured by gel permeation chromatography (GPC) and converted using the calibration curve by standard polystyrene.
  • the content of the thermoplastic resin may be, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more or 20% by mass or more, and 70% by mass or less, based on the total mass of the adhesive composition. It may be 60% by mass or less, 50% by mass or less, or 40% by mass or less, and may be 1 to 70% by mass, 5 to 60% by mass, 10 to 50% by mass, or 20 to 40% by mass.
  • the filler examples include non-conductive fillers (for example, non-conductive particles).
  • the filler may be either an inorganic filler or an organic filler.
  • the inorganic filler 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.
  • the organic filler include organic fine particles such as silicone fine particles, methacrylate / butadiene / styrene fine particles, acrylic / silicone fine particles, polyamide fine particles, and polyimide fine particles. These may be used individually by 1 type, or may be used in combination of a plurality of types.
  • the filler may be, for example, silica fine particles.
  • the content of the filler may be, for example, 0.1 to 10% by mass based on the total mass of the adhesive composition.
  • the coupling agent examples include a silane coupling agent having an organic functional group such as a (meth) acryloyl group, a mercapto group, an amino group, an imidazole group and an epoxy group ( ⁇ -glycidoxypropyltrimethoxysilane, etc.) and tetra.
  • examples thereof include a silane compound such as alkoxysilane, a tetraalkoxy titanate derivative, and a polydialkyl titanate derivative. These may be used individually by 1 type, or may be used in combination of a plurality of types.
  • the adhesive composition contains a coupling agent, the adhesiveness can be further improved.
  • the content of the coupling agent may be, for example, 0.1 to 10% by mass based on the total mass of the adhesive composition.
  • the adhesive composition (first adhesive composition and second adhesive composition) has other components such as a softener, an accelerator, an antioxidant, a colorant, a flame retardant, and a thixotropic agent. Other additives may be further included. The content of the other additives may be, for example, 0.1 to 10% by mass based on the total mass of the adhesive composition.
  • the first adhesive composition and the second adhesive composition may contain the same components as each other, or may contain different components.
  • the thickness d1 (distance indicated by d1 in FIG. 1) of the first adhesive layer 3 is, for example, 0.5 ⁇ m or more from the viewpoint of transferability of the solder particles 2 at the time of manufacturing the adhesive film 10 for circuit connection. , 1.0 ⁇ m or more or 2.0 ⁇ m or more.
  • the thickness d1 of the first adhesive layer 3 is, for example, 5.0 ⁇ m or less, 4.0 ⁇ m or less, or 3.0 ⁇ m or less from the viewpoint of being able to capture the solder particles more efficiently at the time of connection. good. From these viewpoints, the thickness d1 of the first adhesive layer 3 may be, for example, 0.5 to 5.0 ⁇ m, 1.0 to 4.0 ⁇ m, or 2.0 to 3.0 ⁇ m.
  • the thickness d2 (distance indicated by d2 in FIG. 1) of the second adhesive layer 4 may be appropriately set according to the height of the electrodes of the circuit members to be connected and the like.
  • the thickness d2 of the second adhesive layer 4 can sufficiently fill the space between the electrodes to seal the electrodes, and from the viewpoint of obtaining better connection reliability, for example, 0.5 ⁇ m or more. , 1.0 ⁇ m or more or 2.0 ⁇ m or more, 10 ⁇ m or less, 5.0 ⁇ m or less, 4.0 ⁇ m or less or 3.0 ⁇ m or less, 0.5 to 10 ⁇ m, 0.5 to 5.0 ⁇ m , 1.0 to 4.0 ⁇ m or 2.0 to 3.0 ⁇ m.
  • the thickness d1 of the first adhesive layer 3 and the thickness d2 of the second adhesive layer are determined by, for example, sandwiching the circuit connection adhesive film 10 between two pieces of glass (thickness: about 1 mm) and bisphenol A.
  • a resin composition consisting of 100 g of a mold epoxy resin (trade name: jER811, manufactured by Mitsubishi Chemical Co., Ltd.) and 10 g of a curing agent (trade name: Epomount curing agent, manufactured by Refine Tech Co., Ltd.), use a polishing machine. It can be obtained by polishing the cross section using a scanning electron microscope (SEM, trade name: SE-8020, manufactured by Hitachi High-Tech Science Co., Ltd.).
  • solder particles have, for example, a melting point lower than the connection temperature. Therefore, the solder particles are melted by thermocompression bonding at the time of connection and fixed on the electrode. As a result, the opposing electrodes are electrically connected to each other.
  • the melting point of the solder particles may be, for example, 280 ° C. or lower, 220 ° C. or lower, 180 ° C. or lower, 160 ° C. or lower, or 140 ° C. or lower from the viewpoint of enabling mounting at a low temperature.
  • the melting point of the solder particles is, for example, 100 ° C. or higher.
  • 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.
  • tin alloy for example, In—Sn alloy, In—Sn—Ag alloy, Sn—Au alloy, Sn—Bi alloy, Sn—Bi—Ag alloy, Sn—Ag—Cu alloy, Sn—Cu alloy and the like are used. be able to. Specific examples of these tin alloys include the following examples.
  • the indium alloy for example, an In—Bi alloy, an In—Ag alloy, or the like can be used. Specific examples of these indium alloys include the following examples. -In-Bi (In66.3% by mass, Bi33.7% by mass, melting point 72 ° C.) -In-Bi (In33.0% by mass, Bi67.0% by mass, melting point 109 ° C) In-Ag (In97.0% by mass, Ag3.0% by mass, melting point 145 ° C) The above-mentioned indium alloy containing tin shall be classified as a tin alloy.
  • the solder particles are In—Bi alloys, In—Sn alloys, In—Sn—Ag alloys, Sn—Au alloys, Sn—Bi alloys from the viewpoint of obtaining higher reliability during high temperature and high humidity tests and thermal shock tests.
  • Sn-Bi-Ag alloy, Sn-Ag-Cu alloy and Sn-Cu alloy may contain at least one selected from the group.
  • the tin alloy or indium alloy may be selected according to the intended use (temperature at the time of use) of the solder particles. For example, when solder particles are used for fusion at a low temperature, if an In—Sn alloy or a Sn—Bi alloy is used, the solder particles can be fused at 150 ° C. or lower. When a material having a high melting point such as a Sn—Ag—Cu alloy or a Sn—Cu alloy is used, high reliability can be maintained even after being left at a high temperature.
  • the solder particles may contain one or more selected from Ag, Cu, Ni, Bi, Zn, Pd, Pb, Au, P and B.
  • the melting point of the solder particles can be lowered to about 220 ° C., and the bonding strength with the electrode is further improved, so that better conduction reliability can be easily obtained.
  • the Cu content of the solder particles is, for example, 0.05 to 10% by mass, and may be 0.1 to 5% by mass or 0.2 to 3% by mass.
  • the Cu content is 0.05% by mass or more, it becomes easy to achieve better solder connection reliability.
  • the Cu content is 10% by mass or less, the melting point is low and the solder particles tend to have excellent wettability, and as a result, the connection reliability of the joint portion by the solder particles tends to be good.
  • the Ag content of the solder particles is, for example, 0.05 to 10% by mass, and may be 0.1 to 5% by mass or 0.2 to 3% by mass.
  • the Ag content is 0.05% by mass or more, it becomes easy to achieve better solder connection reliability.
  • the Ag content is 10% by mass or less, the solder particles have a low melting point and excellent wettability, and as a result, the connection reliability of the joint portion by the solder particles tends to be good.
  • the solder particles may have a flat surface on a part of the surface.
  • a wide contact area can be secured between the flat surface portion and the electrode by contacting the flat surface portion of the solder particles with the electrode.
  • adjustment is made so that a flat portion of solder particles is arranged on the latter electrode side. By doing so, the connection between the two electrodes can be suitably performed.
  • the surface of the solder particles other than the flat surface portion may be spherical crown-shaped.
  • the solder particles may have a flat surface portion and a spherical crown-shaped curved surface portion.
  • the solder particles may have a shape in which a flat surface portion having a diameter B is formed on a part of the surface of a sphere having a diameter A.
  • the solder particles When the solder particles have a shape in which a flat portion having a diameter B is formed on a part of the surface of a sphere having a diameter A, the solder particles have a diameter A with respect to the diameter A from the viewpoint of achieving better conduction reliability and insulation reliability.
  • the ratio (B / A) of the diameter B of the flat surface portion may be, for example, more than 0.01 and less than 1.0 (0.01 ⁇ B / A ⁇ 1.0), and may be 0.1 to 0.9. You may.
  • the diameter A of the solder particles and the diameter B of the flat surface portion can be observed by, for example, a scanning electron microscope or the like. Specifically, arbitrary solder particles are observed with a scanning electron microscope, and an image is taken.
  • the diameter A of the solder particles and the diameter B of the flat surface portion are measured, and the B / A of the particles is obtained. This operation is performed on 300 solder particles to calculate an average value, which is used as the B / A of the solder particles.
  • solder particles When a quadrangle circumscribing the projected image of solder particles is created by two pairs of parallel lines, and the distances between the opposite sides are X and Y (where Y ⁇ X), respectively, the ratio of Y to X (Y / X). ) May be more than 0.8 and 1.0 or less (0.8 ⁇ Y / X ⁇ 1.0), and may be more than 0.8 and less than 1.0 or 0.81 to 0.99. ..
  • Such solder particles can be said to be particles closer to a true sphere. When the solder particles have a shape close to a true sphere, the solder particles tend to be easily accommodated in the recesses of the substrate in the manufacturing method described later.
  • solder particles have a shape close to a true sphere, the contact between the solder particles and the electrodes is less likely to be uneven and stable when electrically connecting a plurality of opposing electrodes via a solder layer. Tends to get a connection.
  • the projected image of the solder particles can be obtained, for example, by observing any solder particles with a scanning electron microscope.
  • Y / X draw two pairs of parallel lines on the obtained projected image, one pair of parallel lines is at the position where the distance between the parallel lines is the minimum, and the other pair of parallel lines is the distance between the parallel lines. Place in the position where is the maximum. This operation is performed on 300 solder particles to calculate the average value of Y / X, which is used as the Y / X of the solder particles.
  • the average particle size of the solder particles is 1 to 30 ⁇ m.
  • the average particle size of the solder particles may be 2 ⁇ m or more or 4 ⁇ m or more from the viewpoint that excellent conductivity can be easily obtained.
  • the average particle size of the solder particles may be 25 ⁇ m or less or 20 ⁇ m or less from the viewpoint that better connection reliability to a micro-sized electrode can be easily obtained. From these viewpoints, the average particle size of the solder particles may be 2 to 25 ⁇ m or 4 to 20 ⁇ m.
  • the average particle size of the solder particles can be measured using various methods according to the size. For example, a dynamic light scattering method, a laser diffraction method, a centrifugal sedimentation method, an electrical detection band method, a resonance type mass measurement method, or the like can be used. Further, a method of measuring the particle size from an image obtained by an optical microscope, an electron microscope, or the like can be used. Specific examples include a flow-type particle image analyzer, a microtrack, a Coulter counter, and the like.
  • the particle diameter of the non-spherical solder particles may be the diameter of a circle circumscribing the solder particles in the SEM image.
  • C. of the particle size of the solder particles. V. The value is 20% or less.
  • Particle size C.I. V. The value is a value calculated by dividing the standard deviation of the particle size of the solder particles by the average particle size by 100, and is a parameter indicating the degree of variation in the particle size of the solder particles.
  • a small value means that there is little variation in the particle size of the solder particles.
  • the standard deviation of the particle size of the solder particles can be measured by the same method as the above-mentioned method for measuring the average particle size of the solder particles. C. of the particle diameter of the solder particles. V.
  • the value may be 10% or less, 9% or less, 8% or less, 7% or less, or 5% or less from the viewpoint of achieving better conductivity reliability and insulation reliability.
  • V. The lower limit of the value is not particularly limited, and may be, for example, 0.1% or more, 1% or more, or 2% or more. That is, C.I. V.
  • the value may be 0.1 to 20%, 1 to 10%, 2 to 9%, 2 to 8% and the like.
  • the content of the solder particles is, for example, 40% by mass or more, 50% by mass or more, or 60% by mass or more based on the total mass of the adhesive film for circuit connection from the viewpoint of further improving the conductivity. It's okay.
  • the content of the solder particles may be, for example, 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total mass of the circuit connection adhesive film, from the viewpoint of easily suppressing a short circuit. From these viewpoints, the content of the solder particles may be, for example, 40 to 80% by mass, 50 to 75% by mass, or 60 to 70% by mass, based on the total mass of the adhesive film for circuit connection.
  • the particle density of the solder particles in the circuit connection adhesive film 10 is 100 pieces / mm 2 or more, 1000 pieces / mm 2 or more, 3000 pieces / mm 2 or more or 5000 pieces / mm from the viewpoint of obtaining stable connection resistance. It may be 2 or more.
  • the particle density of the solder particles in the circuit connection adhesive film 10 is 100,000 pieces / mm 2 or less, 70,000 pieces / mm 2 or less, 50,000 pieces / mm 2 or less, or 30,000 from the viewpoint of improving the insulating property between adjacent electrodes. Pieces / mm 2 or less may be used.
  • the circuit connection adhesive film 10 has, for example, a substrate on which a plurality of solder particles 2 are arranged on the surface (for example, has a plurality of recesses on the surface, and the solder particles 2 are arranged in at least a part of the plurality of recesses.
  • the first adhesive layer is provided by preparing the soldered substrate (preparation step) and providing the first adhesive layer 3 on the surface (for example, the surface on which the recess is formed) of the substrate. It can be manufactured by a method including transferring solder particles to 3 (transfer step) and providing a second adhesive layer 4 on one surface of the first adhesive layer 3 (lamination step). can. According to this method, by using a substrate in which solder particles are arranged in a predetermined arrangement in advance, it is possible to obtain a circuit connection adhesive film 10 having a predetermined arrangement and having an excellent monodispersity.
  • FIG. 4 is a diagram schematically showing a vertical cross section of a substrate used in the method for manufacturing the adhesive film 10 for circuit connection
  • FIG. 5 is a diagram showing a modified example of the cross-sectional shape of the concave portion of the substrate of FIG.
  • FIG. 6 is a cross-sectional view schematically showing a state in which the solder particles 2 are arranged in the recesses of the substrate of FIG. 4
  • FIG. 7 is a cross-sectional view schematically showing an example of the preparation process.
  • 8 is a cross-sectional view schematically showing an example of the transfer process.
  • a substrate having a plurality of recesses on the surface and solder particles 2 arranged in at least a part of the plurality of recesses is used as the substrate, but the substrate is not limited to such a substrate.
  • a substrate having a support portion (needle or the like) on which solder particles can be fixed can be used.
  • a substrate 6 having a plurality of recesses 7 on the surface is prepared (see FIG. 4).
  • the substrate 6 has a plurality of recesses 7.
  • the plurality of recesses 7 are regularly arranged, for example, in a predetermined pattern (for example, a pattern corresponding to an electrode pattern of a circuit member).
  • a predetermined pattern for example, a pattern corresponding to an electrode pattern of a circuit member.
  • the recess 7 of the substrate 6 may be formed in a tapered shape in which the opening area expands from the bottom 7a side of the recess 7 toward the surface 6a side of the substrate 6. That is, the width of the bottom portion 7a of the recess 7 (width a in FIG. 4) may be narrower than the width of the opening of the recess 7 (width b in FIG. 4).
  • the size of the recess 7 can be set according to the size of the target solder particles and the position of the solder particles in the circuit connection adhesive film. For example, the width (width b) of the opening of the recess 7 may be larger than the maximum particle diameter of the solder particles 2 and may be less than twice the maximum particle diameter of the solder particles.
  • the shape of the recess 7 (the cross-sectional shape of the recess 7) in the vertical cross section of the substrate 6 may be, for example, the shape shown in FIGS. 5A to 5H.
  • the width (width b) of the opening of the recess 7 is the maximum width in the cross-sectional shape.
  • the shape of the opening of the recess 7 may be a circle, an ellipse, a triangle, a quadrangle, a polygon, or the like.
  • the recess 7 of the substrate 6 can be formed by a known method such as lithography or machining. In these methods, the size and shape of the recess can be freely designed.
  • the solder particles 2 can be arranged in the recesses 7 of the substrate 6 by forming the solder particles 2 in the recesses 7 of the substrate 6. In this case, the solder particles 2 can be arranged in the recesses 7 of the substrate 6. May have heat resistance that does not deteriorate with the melting temperature of the fine particles used for forming the solder particles 2.
  • solder particles 2 are arranged (accommodated) in at least a part (part or all) of the plurality of recesses 7 of the substrate 6 (see FIG. 6).
  • the method of arranging the solder particles 2 is not particularly limited.
  • the arrangement method may be either dry type or wet type.
  • the solder particles 2 are placed on the surface 6a of the substrate 6, and the surface 6a of the substrate 6 is rubbed with a squeegee or a fine adhesive roller to remove the excess solder particles 2 and the solder particles in the recesses 7. 2 can be placed.
  • the width b of the opening of the recess 7 is larger than the depth of the recess 7, solder particles may pop out from the opening of the recess 7.
  • a squeegee is used, the solder particles protruding from the opening of the recess 7 are removed.
  • solder particles As a method for removing excess solder particles, there is also a method of rubbing the surface 6a of the substrate 6 with a non-woven fabric or a bundle of fibers by blowing compressed air. Since these methods have a weaker physical force than the squeegee, they are preferable for handling easily deformable particles (for example, solder particles) as solder particles.
  • the solder particles 2 may be arranged in the recess 7 by forming the solder particles 2 in the recess 7 of the substrate 6. Specifically, for example, as shown in FIG. 7, after the fine particles 8 for forming the solder particles 2 are housed in the recess 7, the fine particles 8 housed in the recess 7 are fused to form the recess 7. Solder particles 2 can be formed inside. The fine particles 8 housed in the recess 7 are united by melting and spheroidized by surface tension. At this time, the molten metal follows the bottom 7a at the contact portion with the bottom 7a of the recess 7. It becomes a shape. Therefore, for example, when the bottom portion 7a of the recess 7 has a flat shape as shown in FIG. 7, the solder particles 2 have a flat surface portion 2a as a part of the surface surface.
  • the fine particles 8 may be accommodated in the recesses 7, and the particle size distribution may vary widely or the shape may be distorted.
  • Examples of the method of melting the fine particles 8 contained in the recess 7 include a method of heating the fine particles 8 to a temperature equal to or higher than the melting point of the material (solder) forming the fine particles.
  • the fine particles 8 may not melt, do not spread, or do not coalesce even when heated at a temperature equal to or higher than the melting point due to the influence of the oxide film. Therefore, the fine particles 8 are exposed to a reducing atmosphere, the surface oxide film of the fine particles 8 is removed, and then the fine particles 8 are heated to a temperature equal to or higher than the melting point of the fine particles 8 to melt the fine particles 8 and spread them wet to unify them. Can be done. From the same viewpoint, the fine particles 8 may be melted in a reducing atmosphere.
  • the method for creating a reducing atmosphere is not particularly limited as long as the above effect can be obtained, and for example, there is a method using hydrogen gas, hydrogen radical, formic acid gas and the like.
  • a hydrogen reduction furnace, a hydrogen radical reduction furnace, a formic acid reduction furnace, or a conveyor furnace or a continuous furnace thereof the fine particles 8 can be melted in a reducing atmosphere.
  • These devices may be equipped with a heating device, a chamber filled with an inert gas (nitrogen, argon, etc.), a mechanism for evacuating the inside of the chamber, etc., which makes it easier to control the reduced gas. Become. Further, if the inside of the chamber can be evacuated, the voids can be removed by reducing the pressure after the fine particles 8 are melted and united, and the solder particles 2 having further excellent connection stability can be obtained.
  • the profile of the reduction of the fine particles 8, the melting conditions, the temperature, the adjustment of the atmosphere in the furnace, etc. may be appropriately set in consideration of the melting point of the fine particles 8, the particle size, the size of the recess, the material of the substrate 6, and the like.
  • solder particles 2 having a substantially uniform size can be formed regardless of the material and shape of the fine particles 8. Further, since the size and shape of the solder particles 2 depend on the amount of fine particles 8 accommodated in the recesses 7, the shape of the recesses 7, and the like, the solder particles 2 are designed by designing the recesses 7 (adjusting the size, shape, etc. of the recesses). The size and shape can be freely designed, and solder particles having the desired particle size distribution (solder particles having an average particle size of 1 to 30 ⁇ m and a CV value of the particle size of 20% or less) can be easily produced. I can prepare.
  • solder particles 2 are indium-based solder particles. That is, indium-based solder can be deposited by plating, but it is difficult to precipitate it in the form of particles, and it is a soft and difficult material to handle.
  • indium-based solder fine particles as a raw material, indium-based solder particles having a substantially uniform particle size can be easily produced.
  • the substrate 6 can be handled with the solder particles 2 arranged (accommodated) in the recesses 7. For example, when the substrate 6 is transported and stored in a state where the solder particles 2 are arranged (accommodated) in the recess 7, the deformation of the solder particles 2 can be prevented. Further, in the state where the solder particles 2 are arranged (accommodated) in the recess 7, the solder particles 2 can be easily taken out, so that deformation when the solder particles 2 are collected, surface-treated, or the like can be easily prevented.
  • solder particles 2 are transferred to the first adhesive layer 3 by providing the first adhesive layer 3 on the surface of the substrate 6 (the surface on which the recess 7 is formed) (FIG. 8). reference).
  • a first adhesive layer 3 is formed on the support 11 to obtain a laminated film 12, and then a surface (surface of the substrate 6) 6a on which a recess 7 of the substrate 6 is formed. And the surface of the laminated film 12 on the side of the first adhesive layer 3 (the surface of the first adhesive layer 3 on the side opposite to the support 11) are opposed to each other, and the substrate 6 and the first adhesive layer are opposed to each other. Bring it closer to 3 (see (a) in FIG. 8).
  • the laminated film 12 and the substrate 6 are bonded to each other to bring the first adhesive layer 3 into contact with the surface (the surface on which the recess 7 is formed) 6a of the substrate 6, and the first adhesive layer 3 is brought into contact with the surface (the surface on which the recess 7 is formed) 6a.
  • the solder particles 2 are transferred to.
  • a particle transfer layer 13 including the first adhesive layer 3 and the solder particles 2 having at least a part embedded in the first adhesive layer 3 is obtained (see (b) of FIG. 8). ).
  • solder particles 2 when the bottom portion of the recess 7 is flat, the solder particles 2 have the flat surface portion 2a corresponding to the shape of the bottom portion of the recess 7 and the flat surface portion. 2a is placed in the first adhesive layer 3 with the 2a facing away from the support 11.
  • the first adhesive layer 3 is a varnish composition (varnish-like) prepared by dissolving or dispersing the constituents of the first adhesive layer 3 in an organic solvent by stirring and mixing, kneading and the like. It can be formed using the first adhesive composition). Specifically, for example, the varnish composition is applied onto the support 11 (for example, a base material that has been subjected to a mold release treatment) using a knife coater, a roll coater, an applicator, a comma coater, a die coater, or the like, and then heated. The first adhesive layer 3 can be formed by volatilizing the organic solvent. 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 varnish composition for example, a base material that has been subjected to a mold release treatment
  • the organic solvent used in the preparation of the varnish composition is not particularly limited as long as it has the property of being able to dissolve or disperse each component substantially uniformly.
  • examples of such an organic solvent include toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, butyl acetate and the like. These organic solvents can be used alone or in combination of two or more.
  • Stirring and mixing or kneading in the preparation of the varnish composition can be carried out by using, for example, a stirrer, a raider, a three-roll, 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 the organic solvent is volatilized.
  • the support 11 may be a plastic film or a metal foil.
  • Examples of the support 11 include stretched polypropylene (OPP), polyethylene terephthalate (PET), polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate, polyolefin, polyacetate, polycarbonate, polyphenylene sulfide, polyamide, polyimide, cellulose, and ethylene.
  • a substrate (for example, a film) made of a vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, a synthetic rubber, a liquid crystal polymer, or the like may be used.
  • the heating conditions for volatilizing the organic solvent from the varnish composition applied to the base material can be appropriately set according to the organic solvent to be used and the like.
  • the heating conditions may be, for example, 40 to 120 ° C. for 0.1 to 10 minutes.
  • a part of the solvent may remain on the first adhesive layer 3 without being removed.
  • the content of the solvent in the first adhesive layer 3 may be, for example, 10% by mass or less based on the total mass of the first adhesive layer 3.
  • Examples of the method of laminating the laminated film 12 and the substrate 6 include a heat press, a roll laminating, and a vacuum laminating method. Lamination can be performed, for example, under temperature conditions of 0 to 80 ° C.
  • the first adhesive layer 3 may be formed by directly applying the varnish composition to the substrate 6, but by using the laminated film 12 as in the above method, the support 11 and the first layer may be formed. It becomes easy to obtain the particle transfer layer 13 in which the adhesive layer 3 of 1 and the solder particles 2 are integrated.
  • the second adhesive layer 4 is provided on the surface of the first adhesive layer 3 opposite to the support 11 (the side on which the solder particles 2 are transferred). As a result, the circuit connection adhesive film 10 shown in FIG. 1 is obtained.
  • the constituent components of the second adhesive layer 4 are dissolved or kneaded in an organic solvent by stirring and mixing, kneading, or the like.
  • the first is similar to the method of providing the first adhesive layer 3 on the substrate 6, except that a varnish composition (a varnish-like second adhesive composition) prepared by dispersion is used. It can be provided on the adhesive layer 3. That is, the second adhesive layer is placed on the first adhesive layer 3 by adhering the laminated film obtained by forming the second adhesive layer 4 on the support and the first adhesive layer 3. 4 may be provided, and the second adhesive layer 4 may be provided on the first adhesive layer 3 by directly applying the varnish-like second adhesive composition to the first adhesive layer 3. good.
  • the second adhesive layer 4 may be provided on the surface on the side where the support 11 is provided after the support 11 is peeled off, but the support 11 is as described in the above method. By providing the second adhesive layer 4 on the opposite surface, it can be expected to improve the adhesiveness of the adhesive film for circuit connection to the circuit member and suppress the peeling at the time of connection.
  • the adhesive film 1 in the circuit connection adhesive film 10 may be composed of only the first adhesive layer 3, and other than the first adhesive layer 3 and the second adhesive layer 4. An adhesive layer may be further provided.
  • connection structure (circuit connection structure) using the above-mentioned circuit connection adhesive film 10 as a connection material and a method for manufacturing the same will be described.
  • FIG. 9 is a schematic cross-sectional view showing an embodiment of the connection structure.
  • the 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 21a of the first circuit board 21.
  • the second circuit board 26 having the second electrode 25 formed on the main surface 24a of the second circuit board 24 and the second circuit board 24, and the first electrode 22 and the second electrode 25 are provided. It includes a connecting portion 27 that is electrically connected to each other via the solder layer 30 and that adheres the first circuit member 23 and the second circuit member 26.
  • the first circuit member 23 and the second circuit member 26 may be the same or different from each other.
  • the first circuit member 23 and the second circuit member 26 are a glass substrate or a plastic substrate on which a circuit electrode is formed; a printed wiring board; a ceramic wiring board; a flexible wiring board; an IC chip such as a drive IC, or the like. It's okay.
  • the first circuit board 21 and the second circuit board 24 may be made of an inorganic substance such as semiconductor, glass, or ceramic, an organic substance such as polyimide or polycarbonate, or a composite such as glass / epoxy.
  • the first circuit board 21 may be a plastic substrate.
  • the first circuit member 23 may be, for example, a plastic substrate (a plastic substrate made of an organic substance such as polyimide, polycarbonate, polyethylene terephthalate, or cycloolefin polymer) on which a circuit electrode is formed, and may be a second circuit.
  • the member 26 may be, for example, an IC chip such as a drive IC.
  • a display region is formed by regularly arranging a pixel drive circuit such as an organic TFT or a plurality of organic EL elements R, G, and B on the plastic substrate in a matrix. It may be the one.
  • the first electrode 22 and the second electrode 25 are gold, silver, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, aluminum, molybdenum, titanium and other metals, indium tin oxide (ITO), and the like.
  • the electrode may be an electrode containing an oxide such as indium zinc oxide (IZO) or indium gallium zinc oxide (IGZO).
  • the first electrode 22 and the second electrode 25 may be electrodes formed by laminating two or more of these metals, oxides, and the like.
  • the electrode formed by stacking two or more types may have two or more layers, and may have three or more layers.
  • the first electrode 22 and the second electrode 25 may be circuit electrodes or bump electrodes. In FIG. 9, the first electrode 22 is a circuit electrode and the second electrode 25 is a bump electrode.
  • the total height of the first electrode 22 and the height of the second electrode 25 is smaller than the average particle diameter of the solder particles 2 in the circuit connection adhesive film used to form the connection portion 27. good.
  • the total value may be, for example, 30 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 5 ⁇ m or less, less than 4 ⁇ m, less than 3 ⁇ m, less than 2 ⁇ m, or less than 1 ⁇ m.
  • the height of the first electrode 22 (for example, the height of the circuit electrode) may be, for example, 0.05 to 5.0 ⁇ m, 0.1 to 4.0 ⁇ m, or 0.5 to 3.0 ⁇ m.
  • the height of the second electrode 25 (for example, the height of the bump electrode) may be, for example, 0.5 to 25.0 ⁇ m, 2.0 to 15.0 ⁇ m, or 5.0 to 10.0 ⁇ m.
  • connection portion 27 is a cured product of the circuit connection adhesive film 10.
  • the connecting portion 27 is located, for example, on the side of the first circuit member 23 in the direction in which the first circuit member 23 and the second circuit member 26 face each other (hereinafter referred to as “opposing direction”), and the first adhesive is used.
  • a solder layer 30 that is interposed between the electrodes 22 and the second electrode 25 and electrically connects the first electrode 22 and the second electrode 25 to each other, and solder particles 2 located between the adjacent electrodes are provided. Have.
  • the solder particles 2 may be in a molten state in the connecting portion 27.
  • the connection portion 27 does not have to have two distinct regions between the first region 28 and the second region 29, for example, the first adhesive layer 3 and the second adhesive. It may include a hardened region in which the layer 4 is mixed.
  • connection structure examples include a color display in which a plastic substrate in which fine LED elements (light emitting elements) are regularly arranged, a drive circuit element which is a driver for displaying an image, and a fine LED element are connected.
  • Examples thereof include a micro LED display device such as a touch panel in which a regularly arranged plastic substrate and a position input element such as a touch pad are connected.
  • the connection structure may be an organic EL display device in which the LED element is an organic EL element.
  • the connection structure can also be applied to various monitors such as smart phones, tablets, televisions, vehicle navigation systems, wearable terminals, furniture; home appliances; daily necessities and the like.
  • FIG. 10 is a schematic cross-sectional view showing an embodiment of a method for manufacturing the connection structure 100.
  • FIG. 10A and FIG. 10B are schematic cross-sectional views showing each step.
  • a surface on which the first electrode 22 of the first circuit member 23 is provided and a second electrode 25 of the second circuit member 26 are provided in the method of manufacturing the connection structure 100.
  • a laminate including the above-mentioned circuit connection adhesive film 10 and the first circuit member 23, the circuit connection adhesive film 10, and the second circuit member 26 are arranged between the surfaces. Is heated in a state of being pressed in the thickness direction of the laminated body, whereby the first electrode 22 and the second electrode 25 are electrically connected to each other via the solder layer 30, and the first circuit member 23 is connected. Includes bonding the second circuit member 26 to the second circuit member 26.
  • the first circuit board 23 including the first electrode 22 formed on the main surface 21a of the first circuit board 21 and the first circuit board 21, and the second circuit board 24.
  • 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 are arranged.
  • a circuit connection adhesive film 10 is placed between the 26 and the 26.
  • the circuit connection adhesive film 10 is placed on the first circuit member so that the first adhesive layer 3 side faces the main surface 21a of the first circuit board 21. Laminate on 23.
  • the circuit connection adhesive film 10 was laminated so that the first electrode 22 on the first circuit board 21 and the second electrode 25 on the second circuit board 24 face each other.
  • the second circuit member 26 is arranged on the first circuit member 23.
  • FIG. 10B a laminate in which the first circuit member 23, the circuit connection adhesive film 10, and the second circuit member 26 are laminated in this order is laminated.
  • the first circuit member 23 and the second circuit member 26 are thermocompression-bonded to each other.
  • the fluidable uncured thermosetting components contained in the first adhesive layer 3 and the second adhesive layer 4 are adjacent to each other. It flows so as to fill the voids between the electrodes (the voids between the first electrodes 22 and the voids between the second electrodes 25), and is cured by the above heating.
  • solder particles 2 are melted by being heated in a pressed state and gather together between the first electrode 22 and the second electrode 25 to form a solder layer 30, which is then cooled.
  • the solder layer 30 is fixed between the first electrode 22 and the second electrode 25.
  • the first electrode 22 and the second electrode 25 are electrically connected to each other via the solder layer 30 (melted solidified product of the solder particles 2), and the first circuit member 23 and the second circuit The members 26 are bonded to each other to obtain the connection structure 100 shown in FIG.
  • the heating temperature at the time of connection may be any temperature as long as the solder particles can be melted (for example, a temperature higher than the melting point of the solder particles), and may be, for example, 130 to 260 ° C.
  • the pressurization is not particularly limited as long as it does not damage the adherend, but for example, the area-equivalent pressure of the chip may be 0.1 to 50 MPa, 40 MPa or less, and 0.1 to 40 MPa. May be. These heating and pressurizing times may be in the range of 0.5 to 300 seconds.
  • A Cationic polymerizable compound
  • A1 Celoxide 8010 (B-7-oxavicyclo [4.1.0] heptane, manufactured by Daicel Corporation)
  • A2 ETERNACOLL OXBP (4,4'-bis [3-ethyl-3-oxetanyl] methoxymethyl] biphenyl, manufactured by Ube Kosan Co., Ltd.)
  • A3 jER1010 (bisphenol A type solid epoxy resin, manufactured by Mitsubishi Chemical Corporation)
  • B Thermal cation polymerization initiator (thermal latent cation generator)
  • B1 CXC-1821 (Quaternary ammonium salt type thermoacid generator, manufactured by King Industries)
  • C1 Thermoplastic resin
  • P-1 fluorene-type phenoxy resin synthesized by the method described later
  • C2 YP-70 (bisphenol A / bisphenol F copolymerized phenoxy resin, manufactured by Nittetsu Chemical & Materials Co., Ltd.)
  • D Filler
  • D1 Aerosil R805 (hydrolyzed product of trimethoxyoctylsilane and silica (silica fine particles), manufactured by Evonik Industries AG, diluted to 10% by mass of non-volatile content with an organic solvent)
  • D2 Surface-treated silica particles (hydrolysis product of silica and bis (trimethylsilyl) amine)
  • E Coupling agent
  • KBM-403 ⁇ -glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • ⁇ Preparation of substrate> Prepare a substrate (A) (PET film, thickness: 55 ⁇ m), a substrate (B) (PET film, thickness: 54 ⁇ m) and a substrate (C) (PET film, thickness: 57 ⁇ m) having a plurality of recesses on the surface. did.
  • the concave portion of the substrate (A) has a truncated cone shape in which the opening area expands toward the surface side of the substrate (when viewed from the upper surface of the opening, the center of the bottom and the center of the opening are the same), and the opening diameter is 4.3 ⁇ m ⁇ .
  • the bottom diameter was 4.0 ⁇ m ⁇ and the depth was 4.0 ⁇ m.
  • the plurality of recesses of the substrate (A) were regularly formed in a three-way arrangement at an interval of 6.2 ⁇ m (distance between the centers of the bottoms) so as to be 29,000 per 1 mm square.
  • the concave portion of the substrate (B) has a truncated cone shape in which the opening area expands toward the surface side of the substrate (when viewed from the upper surface of the opening, the center of the bottom and the center of the opening are the same), and the opening diameter is 3.3 ⁇ m ⁇ .
  • the bottom diameter was 3.0 ⁇ m ⁇ and the depth was 3.0 ⁇ m.
  • the plurality of recesses were regularly formed in a three-way arrangement at an interval of 6.2 ⁇ m (distance between the centers of the bottoms) so as to be 29,000 per 1 mm square.
  • the concave portion of the substrate (C) has a truncated cone shape in which the opening area expands toward the surface side of the substrate (when viewed from the upper surface of the opening, the center of the bottom and the center of the opening are the same), and the opening diameter is 5.3 ⁇ m ⁇ .
  • the bottom diameter was 5.0 ⁇ m ⁇ and the depth was 5.0 ⁇ m.
  • the plurality of recesses were regularly formed in a three-way arrangement at an interval of 6.2 ⁇ m (distance between the centers of the bottoms) so as to be 29,000 per 1 mm square.
  • Examples 1 to 8, Comparative Examples 1 to 6 The anisotropic conductive adhesion of Examples 1 to 8 and Comparative Examples 1 to 6 comprising an adhesive film having the composition shown in Table 1 and conductive particles arranged in the adhesive film by the method shown below.
  • An agent film was prepared.
  • the step (a) the step (a1) was carried out in Examples 1 to 5, Comparative Examples 1 to 3 and Comparative Example 5, and the step (a2) was carried out in Example 6, and Examples 7 and Comparative Example were carried out.
  • the step (a3) was carried out, in Example 8, the step (a4) was carried out, and in Comparative Example 6, the step (a5) was carried out.
  • Step (a): Preparation step) [Step (a1): Preparation and arrangement of solder particles (type: F1, average particle diameter: 4.0 ⁇ m)] 100 g of Sn-Bi solder fine particles (manufactured by 5N Plus, melting point 138 ° C., Type 8) were immersed in distilled water, ultrasonically dispersed, and then leveled to recover the solder fine particles floating in the supernatant. This operation was repeated to recover 10 g of solder fine particles. The average particle size of the obtained solder fine particles was 1.0 ⁇ m, and the particle size was C.I. V. The value was 42%.
  • solder fine particles (average particle diameter: 1.0 ⁇ m, CV value of particle diameter: 42%) were placed on the surface of the substrate (A) where the recesses were formed.
  • the surface of the substrate (A) on which the recesses were formed was rubbed with a fine adhesive roller to remove excess solder fine particles, and the solder fine particles were arranged only in the recesses.
  • the substrate in which the solder fine particles are arranged in the recesses is put into a hydrogen radical reduction furnace (hydrogen plasma reflow device manufactured by Shinko Seiki Co., Ltd.), and after evacuation, hydrogen gas is introduced into the furnace to introduce the inside of the furnace. Was filled with hydrogen gas.
  • the temperature inside the furnace was adjusted to 120 ° C., and hydrogen radicals were irradiated for 5 minutes.
  • the hydrogen gas in the furnace is removed by vacuuming, and after heating to 145 ° C, nitrogen is introduced into the furnace to return it to atmospheric pressure, and then the temperature in the furnace is lowered to room temperature to form solder particles. did.
  • solder particles were separately prepared by the same operation, and the obtained solder particles were recovered from the recesses by tapping the back side of the recesses of the substrate. It was confirmed that the solder particles had a flat surface portion on a part of the surface, and the ratio (B / A) of the diameter B of the flat surface portion to the diameter A of the solder particles was 0.35. Further, when a quadrangle circumscribing the projected image of the solder particles was created by two pairs of parallel lines, Y / X was 0.93 when the distance between the opposite sides was X and Y (however, Y ⁇ X). I confirmed that. In addition, the average particle diameter of the solder particles and the C.I. V.
  • the average particle size was 4.0 ⁇ m, and the particle size C.I. V. The value was 7.9%.
  • the particle transfer layer produced in the step (b) was cut out to a size of 10 cm ⁇ 10 cm, and Pt sputtering was applied to the surface on which the solder particles were arranged. After that, it is a value measured by observing 300 solder particles by SEM.
  • solder particles were separately prepared by the same operation, and the obtained solder particles were recovered from the recesses by tapping the back side of the recesses of the substrate. It was confirmed that the solder particles had a flat surface portion on a part of the surface, and the ratio (B / A) of the diameter B of the flat surface portion to the diameter A of the solder particles was 0.40. Further, when a quadrangle circumscribing the projected image of the solder particles was created by two pairs of parallel lines, Y / X was 0.93 when the distance between the opposite sides was X and Y (however, Y ⁇ X). I confirmed that. In addition, the average particle diameter of the solder particles and the C.I. V.
  • the average particle size was 3.0 ⁇ m, and the particle size C.I. V. The value was 8.8%.
  • the particle transfer layer produced in the step (b) was cut out to a size of 10 cm ⁇ 10 cm, and Pt sputtering was applied to the surface on which the solder particles were arranged. After that, it is a value measured by observing 300 solder particles by SEM.
  • solder particles were separately prepared by the same operation, and the obtained solder particles were recovered from the recesses by tapping the back side of the recesses of the substrate. It was confirmed that the solder particles had a flat surface portion on a part of the surface, and the ratio (B / A) of the diameter B of the flat surface portion to the diameter A of the solder particles was 0.44. Further, when a quadrangle circumscribing the projected image of the solder particles was created by two pairs of parallel lines, Y / X was 0.93 when the distance between the opposite sides was X and Y (however, Y ⁇ X). I confirmed that. In addition, the average particle diameter of the solder particles and the C.I. V.
  • the average particle size was 5.0 ⁇ m, and the particle size C.I. V. The value was 7.6%.
  • the particle transfer layer produced in the step (b) was cut out to a size of 10 cm ⁇ 10 cm, and Pt sputtering was applied to the surface on which the solder particles were arranged. After that, it is a value measured by observing 300 solder particles by SEM.
  • Step (a4) Preparation and arrangement of solder particles (type: F2, average particle diameter: 4.0 ⁇ m)] Using Sn-Ag-Cu solder fine particles (manufactured by Mitsui Kinzoku Kogyo Co., Ltd., melting point 219 ° C., ST-3) instead of Sn-Bi solder fine particles, and the temperature before irradiating hydrogen radicals in the hydrogen radical reduction furnace. Solder particles were formed in the same manner as in step (a1), except that the temperature was changed to 200 ° C instead of 120 ° C and the heating temperature after removing the hydrogen gas in the furnace was changed to 225 ° C instead of 145 ° C. Then, a substrate in which conductive particles (solder particles) were arranged in the concave portions, which was used in the step (b2), was prepared.
  • Sn-Ag-Cu solder fine particles manufactured by Mitsui Kinzoku Kogyo Co., Ltd., melting point 219 ° C., ST-3
  • solder particles were separately prepared by the same operation, and the obtained solder particles were recovered from the recesses by tapping the back side of the recesses of the substrate. It was confirmed that the solder particles had a flat surface portion on a part of the surface, and the ratio (B / A) of the diameter B of the flat surface portion to the diameter A of the solder particles was 0.35. Further, when a quadrangle circumscribing the projected image of the solder particles was created by two pairs of parallel lines, Y / X was 0.93 when the distance between the opposite sides was X and Y (however, Y ⁇ X). I confirmed that. In addition, the average particle diameter of the solder particles and the C.I. V.
  • the average particle size was 4.0 ⁇ m, and the particle size C.I. V. The value was 7.9%.
  • the particle transfer layer produced in the step (b) was cut out to a size of 10 cm ⁇ 10 cm, and Pt sputtering was applied to the surface on which the solder particles were arranged. After that, it is a value measured by observing 300 solder particles by SEM.
  • conductive particles type: F3, average particle diameter: 3.9 ⁇ m, particle diameter
  • a CV value: 3.0% and a specific gravity: 2.7) were prepared and placed on the surface of the substrate (A) on which the recesses were formed.
  • the surface of the substrate (A) on which the recesses were formed was rubbed with a fine adhesive roller to remove excess conductive particles, and the conductive particles were arranged only in the recesses.
  • Step (b1): Preparation of First Adhesive Layer The components shown as X1 or X2 in Table 1 were mixed with an organic solvent (2-butanone) in the blending amount (unit: parts by mass, solid content amount) shown in Table 1 to obtain a resin solution. Next, this resin solution was applied to a 38 ⁇ m-thick PET film that had been mold-released from silicone, and dried with hot air at 60 ° C. for 3 minutes to obtain a first adhesive layer having a thickness shown in Tables 2 to 4. Made on film.
  • Step (b2): Transfer of conductive particles The first adhesive layer formed on the PET film produced in the step (b1) and the substrate prepared in the step (a) in which the conductive particles are arranged in the recesses are arranged so as to face each other. Conductive particles were transferred to the adhesive layer of No. 1. As a result, a particle transfer layer was obtained.
  • Step (c1): Preparation of second adhesive layer The components shown as X1 or X2 in Table 1 were mixed with an organic solvent (2-butanone) in the blending amount (unit: parts by mass, solid content amount) shown in Table 1 to obtain a resin solution. Next, this resin solution was applied to a PET film having a thickness of 50 ⁇ m that had been mold-released from silicone, and dried with hot air at 60 ° C. for 3 minutes to obtain a second adhesive layer having a thickness shown in Tables 2 to 4. Made on film.
  • Step (c2): Laminating the second adhesive layer The particle transfer layer prepared in the step (b) and the second adhesive layer prepared in the step (c1) were bonded together while applying a temperature of 50 ° C. As a result, an anisotropic conductive adhesive film was obtained.
  • Tables 2 to 4 show the thickness of the anisotropic conductive adhesive film and the ratio r of the thickness of the anisotropic conductive adhesive film to the average particle diameter of the conductive particles.
  • the calorific value QC when heated and the calorific value QD when heated from 50 ° C to 300 ° C were determined. No increase in calorific value was observed at temperatures above 300 ° C. in any of the anisotropic conductive adhesive films (the rate of change of the differential curve (DDSC curve) of the DSC curve was 0.01 [W ⁇ g ° C.]. ], It was judged that the film was completely cured at 300 ° C. (curing rate 100%).
  • connection resistance and insulation resistance As the first circuit member, Cr (20 nm) / Au (200 nm) is formed on the surface of a non-alkali glass substrate (OA-11, manufactured by Nippon Electric Glass Co., Ltd., outer shape: 76 mm ⁇ 28 mm, thickness: 0.3 mm). A substrate with electrodes (A) having electrodes (electrode size 22 ⁇ m ⁇ 22 ⁇ m, space between electrodes: 8 ⁇ m) was prepared.
  • a sapphire chip in which bump electrodes are arranged (outer shape: 0.5 mm ⁇ 0.5 mm, thickness: 0.2 mm, bump electrode size: 20 ⁇ m ⁇ 20 ⁇ m, space between bump electrodes: 10 ⁇ m, bump Electrode thickness: 1.5 ⁇ m) was prepared.
  • connection structure (A) was produced using the anisotropic conductive adhesive films of Examples 1 to 8 and Comparative Examples 1 to 6. Specifically, first, the anisotropic conductive adhesive film was placed on the first circuit member. Next, using a thermocompression bonding device (LD-06, manufactured by Ohashi Seisakusho Co., Ltd.) consisting of a stage consisting of a ceramic heater and a tool (8 mm ⁇ 50 mm), 50 ° C., 0.98 MPa (10 kgf / cm 2 ).
  • LD-06 thermocompression bonding device
  • the anisotropic conductive adhesive film is attached to the first circuit member by heating and pressurizing for 2 seconds under the conditions of the above conditions, and the release film on the side opposite to the first circuit member side of the anisotropic conductive adhesive film. (PET film) was peeled off. Next, after aligning the bump electrode of the first circuit member and the circuit electrode of the second circuit member, heating and pressurization are performed on a pedestal heated to 30 ° C. at a temperature of 50 ° C. and a pressure of 1 MPa. The anisotropic conductive adhesive film is attached to the second circuit member by starting and raising the temperature to 160 ° C. or 230 ° C. under the condition of 1 ° C./sec while keeping the pressing force substantially constant (1 MPa).
  • connection structure (A) was produced.
  • the temperature is the measured maximum temperature of the anisotropic conductive adhesive film, and the pressure is the value calculated with respect to the chip area of the second circuit member.
  • the temperature rise reached was 160 ° C.
  • Example 8 the temperature rise reached 230 ° C.
  • connection resistance It was carried out by the four-terminal measurement method, and immediately after the production of the connection structure (A) and after being treated in a high-temperature and high-humidity tank with a temperature of 85 ° C and a humidity of 85% RH for 250 hours, the average value of the connection resistance values measured at four points. was used to evaluate the connection resistance.
  • a DCC 6240B (trade name) was used as the current generator, and an ADC 7461A (trade name) was used as the digital multimeter.
  • connection resistance When the connection resistance is less than 0.2 ⁇ , it is judged as "S”, when the connection resistance is 0.2 ⁇ or more and less than 0.5 ⁇ , it is judged as “A”, and when the connection resistance is 0.5 ⁇ or more, it is judged as "A”. It was judged as "D”.
  • S When the connection resistance is less than 0.2 ⁇ , it is judged as "S”, when the connection resistance is 0.2 ⁇ or more and less than 0.5 ⁇ , it is judged as "A”, and when the connection resistance is 0.5 ⁇ or more, it is judged as "A”. It was judged as "D”.
  • Tables 5 and 6 The results are shown in Tables 5 and 6.
  • connection structure (A) was manufactured and after being treated in a high-temperature and high-humidity tank with a temperature of 85 ° C. and a humidity of 85% RH for 250 hours, the insulation resistance was evaluated using the minimum insulation resistance values measured at four locations. ..
  • As the insulation resistance tester SM7120 (trade name) manufactured by Hioki Electric Co., Ltd. was used. When the insulation resistance value is 1.0 ⁇ 10 10 ⁇ or more, it is judged as “S”, and when the insulation resistance value is 1.0 ⁇ 10 9 ⁇ or more and less than 1.0 ⁇ 10 10 ⁇ , it is judged as “A”. When the insulation resistance value was less than 1.0 ⁇ 109 ⁇ , it was evaluated as “D”. The results are shown in Tables 5 and 6.
  • connection structure (B) was produced using the anisotropic conductive adhesive films of Examples 1 to 8 and Comparative Examples 1 to 6.
  • the connection structure (B) is manufactured on the surface of a non-alkali glass substrate (OA-11, manufactured by Nippon Electric Glass Co., Ltd., outer diameter: 76 mm ⁇ 28 mm, thickness: 0.3 mm) as the first circuit member.
  • a substrate with electrodes (B) having an ITO (220 nm) electrode (electrode size 22 ⁇ m ⁇ 22 ⁇ m, space between electrodes: 8 ⁇ m) is prepared, and the substrate with electrodes (B) is used instead of the substrate with electrodes (A). Except for the fact that the connection structure (A) was prepared, the procedure was the same as that for the preparation.
  • the capture rate of the conductive particles captured between the electrodes is based on the following formula.
  • the capture rate of the conductive particles is 70% or more, it is judged as “S”, when the capture rate of the conductive particles is 60% or more and less than 70%, it is judged as "A”, and the capture rate of the conductive particles is 50% or more.
  • it was less than 60% it was evaluated as "B”
  • the capture rate of conductive particles was less than 50% it was evaluated as "D”.

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