WO2022107800A1 - Adhesive film for circuit connection, and connection structure and method for manufacturing same - Google Patents

Adhesive film for circuit connection, and connection structure and method for manufacturing same 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
Application number
PCT/JP2021/042211
Other languages
French (fr)
Japanese (ja)
Inventor
敏光 森谷
邦彦 赤井
勝将 宮地
Original Assignee
昭和電工マテリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to CN202180077955.5A priority Critical patent/CN116529838A/en
Priority to JP2022563795A priority patent/JPWO2022107800A1/ja
Priority to KR1020237019088A priority patent/KR20230109659A/en
Publication of WO2022107800A1 publication Critical patent/WO2022107800A1/en

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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”.

Abstract

A thermosetting adhesive film for circuit connection according to the present invention contains solder particles having an average particle diameter of 1-30 μm with the particle diameter having a CV value of 20% or less. A ratio of the thickness of the adhesive film for circuit connection to the average particle diameter of the solder particles is more than 1.0 and less than 1.5. Assuming that the solder particles have a melting point of Tm°C, the curing rate at Tm°C is 80% or more when heating is performed at a rate of temperature rise of 10°C/minute under a nitrogen atmosphere.

Description

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Adhesive film for circuit connection, connection structure and its manufacturing method
　本発明は、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に関する。 The present invention relates to an adhesive film for circuit connection, a connection structure, and a method for manufacturing the same.
　液晶表示用ガラスパネルに液晶駆動用ＩＣを実装する方式は、ＣＯＧ（Ｃｈｉｐ－ｏｎ－Ｇｌａｓｓ）実装と、ＣＯＦ（Ｃｈｉｐ－ｏｎ－Ｆｌｅｘ）実装との二種に大別することができる。ＣＯＧ実装では、例えば、フィルム状の回路接続用接着剤（以下、「回路接続用接着剤フィルム」という）を用いて液晶駆動用ＩＣを直接ガラスパネル上に接合する。一方、ＣＯＦ実装では、例えば、金属配線を有するフレキシブルテープに液晶駆動用ＩＣを接合し、回路接続用接着剤フィルムを用いてそれらをガラスパネルに接合する。 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. In 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”). On the other hand, in 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.
　ところで、近年の液晶表示の高精細化に伴い、液晶駆動用ＩＣの回路電極である金属バンプは狭ピッチ化及び狭面積化している。そのため、接着剤中の導電粒子が隣り合う回路電極間に流出してショートを発生させるおそれがある。特にＣＯＧ実装ではその傾向が顕著である。また、隣り合う回路電極間に導電粒子が流出すると、金属バンプとガラスパネルとの間に捕捉される導電粒子数が減少し、対向する回路電極間の接続抵抗が上昇する接続不良を起こすおそれがある。 By the way, with the recent increase in the definition of liquid crystal displays, 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. In addition, if conductive particles flow out between adjacent circuit electrodes, 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.
　これらの問題を解決する方法として、導電粒子（母粒子）の表面に複数の絶縁粒子（子粒子）を付着させ、複合粒子（絶縁被覆導電粒子）を形成させる方法が提案されている。例えば、特許文献１では導電粒子の表面に球状の樹脂粒子を付着させる方法が提案されている。 As a method for solving these problems, a method has been proposed in which a plurality of insulating particles (child particles) are attached to the surface of conductive particles (mother particles) to form composite particles (insulation-coated conductive particles). For example, Patent Document 1 proposes a method of adhering spherical resin particles to the surface of conductive particles.
特許第４７７３６８５号公報Japanese Patent No. 4773685
　本発明は、上記のような絶縁被覆導電粒子を用いずとも、導電粒子の充分な捕捉率を確保しつつ、隣り合う電極間の充分な絶縁性を確保することができる、回路接続用接着剤フィルムを提供することを主な目的とする。 INDUSTRIAL APPLICABILITY 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.
　本発明の一側面は、下記［１］に示す回路接続用接着剤フィルムに関する。 One aspect of the present invention relates to the circuit connection adhesive film shown in [1] below.
［１］熱硬化性の回路接続用接着剤フィルムであって、平均粒子径が１～３０μｍであり、粒子径のＣ．Ｖ．値が２０％以下であるはんだ粒子を含有し、前記はんだ粒子の平均粒子径に対する前記回路接続用接着剤フィルムの厚さの比が、１．０超１．５未満であり、前記はんだ粒子の融点をＴｍ℃とすると、窒素雰囲気下、１０℃／分の昇温速度で加熱したときのＴｍ℃での硬化率が８０％以上である、回路接続用接着剤フィルム。 [1] A thermosetting adhesive film for circuit connection, having an average particle size of 1 to 30 μm, 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.
　上記側面の回路接続用接着剤フィルムによれば、導電粒子（はんだ粒子）の充分な捕捉率を確保しつつ、隣り合う電極間の充分な絶縁性を確保することができる。ここで、「捕捉率」とは、回路接続用接着剤フィルムの単位面積当たりの導電粒子（はんだ粒子）の数に対する、接続箇所の単位面積あたりに捕捉された導電粒子の数の割合を意味する。 According to 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). Here, 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. ..
　ところで、近年、マイクロＬＥＤと呼ばれる新技術の開発等に伴い、電極の高さが低い回路部材が使用されるようになってきている。このような回路部材を用いる場合、接続される電極の高さの合計値が、回路接続用接着剤に使用される導電粒子の粒子径よりも小さくなることがある。本発明者らの検討により明らかとなったことであるが、このような接続構造体を製造する場合に上記のような絶縁被覆導電粒子を含有する回路接続用接着剤（例えば回路接続用接着剤フィルム）を用いたとしても、充分な捕捉率と充分な絶縁性とを両立することは難しい。一方、上記側面の回路接続用接着剤フィルムによれば、接続される電極の高さの合計値が導電粒子の粒子径よりも小さい場合であっても、導電粒子（はんだ粒子）の充分な捕捉率を確保しつつ、隣り合う電極間の充分な絶縁性を確保することができる。 By the way, in recent years, with the development of a new technology called a micro LED, a circuit member having a low electrode height has come to be used. When such a circuit member is 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. As has been clarified by the studies of the present inventors, when manufacturing such a connection structure, a circuit connection adhesive containing the above-mentioned insulating coated conductive particles (for example, a circuit connection adhesive) Even if a film) is used, it is difficult to achieve both a sufficient capture rate and a sufficient insulating property. On the other hand, according to 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.
　上記側面の回路接続用接着剤フィルムは、下記［２］～［６］に示す回路接続用接着剤フィルムであってよい。 The circuit connection adhesive film on the side surface may be the circuit connection adhesive film shown in the following [2] to [6].
［２］重合性化合物と、熱重合開始剤とを含有する、［１］に記載の回路接続用接着剤フィルム。 [2] The adhesive film for circuit connection according to [1], which contains a polymerizable compound and a thermal polymerization initiator.
［３］前記重合性化合物が、カチオン重合性化合物であり、前記熱重合開始剤が熱カチオン重合開始剤である、［２］に記載の回路接続用接着剤フィルム。 [3] The adhesive film for circuit connection according to [2], wherein the polymerizable compound is a cationically polymerizable compound, and the thermal polymerization initiator is a thermal cationic polymerization initiator.
［４］前記重合性化合物が、脂環式エポキシ化合物及びオキセタン化合物からなる群より選択される少なくとも一種を含む、［３］に記載の回路接続用接着剤フィルム。 [4] The adhesive film for circuit connection according to [3], wherein the polymerizable compound contains at least one selected from the group consisting of an alicyclic epoxy compound and an oxetane compound.
［５］前記はんだ粒子の融点が、２８０℃以下である、［１］～［４］のいずれかに記載の回路接続用接着剤フィルム。 [5] The adhesive film for circuit connection according to any one of [1] to [4], wherein the solder particles have a melting point of 280 ° C. or lower.
［６］第１の電極を有する第１の回路部材と第２の電極を有する第２の回路部材とを接着すると共に、前記第１の電極と前記第２の電極とを互いに電気的に接続するために用いられ、前記第１の電極の高さと前記第２の電極の高さの合計が、前記はんだ粒子の平均粒子径よりも小さい、［１］～［５］のいずれかに記載の回路接続用接着剤フィルム。 [6] The first circuit member having the first electrode and the second circuit member having the second electrode are adhered to each other, and the first electrode and the second electrode are electrically connected to each other. [1] to [5], wherein the sum of the height of the first electrode and the height of the second electrode is smaller than the average particle diameter of the solder particles. Adhesive film for circuit connection.
　本発明の他の一側面は、下記［７］に示す接続構造体に関する。 Another aspect of the present invention relates to the connection structure shown in [7] below.
［７］第１の電極を有する第１の回路部材と、前記第１の電極と電気的に接続される第２の電極を有する第２の回路部材と、前記第１の電極と前記第２の電極とをはんだ層を介して互いに電気的に接続し且つ前記第１の回路部材と前記第２の回路部材とを接着する接続部と、を備え、前記接続部が、［１］～［６］のいずれかに記載の回路接続用接着剤フィルムの硬化物を含む、接続構造体。 [7] A first circuit member having a first electrode, a second circuit member having a second electrode electrically connected to the first electrode, the first electrode, and the second electrode. 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].
　上記側面の接続構造体は、下記［８］に示す接続構造体であってよい。 The connection structure on the side surface may be the connection structure shown in [8] below.
［８］前記第１の電極の高さと前記第２の電極の高さの合計が、前記はんだ粒子の平均粒子径よりも小さい、［７］に記載の接続構造体。 [8] The connection structure according to [7], wherein the sum of the height of the first electrode and the height of the second electrode is smaller than the average particle diameter of the solder particles.
　本発明の他の一側面は、下記［９］に示す接続構造体の製造方法に関する。 Another aspect of the present invention relates to a method for manufacturing a connection structure shown in the following [9].
［９］第１の電極を有する第１の回路部材の前記第１の電極が設けられている面と、第２の電極を有する第２の回路部材の前記第２の電極が設けられている面との間に、［１］～［６］に記載の回路接続用接着剤フィルムを配置することと、前記第１の回路部材と前記回路接続用接着剤フィルムと前記第２の回路部材とを含む積層体を前記積層体の厚さ方向に押圧した状態で加熱することにより、前記第１の電極と前記第２の電極とをはんだ層を介して互いに電気的に接続し且つ前記第１の回路部材と前記第２の回路部材とを接着することと、を含む、接続構造体の製造方法。 [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 By heating the laminated body containing the above in a state of being pressed in the thickness direction of the laminated body, the first electrode and the second electrode are electrically connected to each other via a solder layer and the first electrode is connected to each other. A method for manufacturing a connection structure, comprising bonding the circuit member of the above to the second circuit member.
　上記側面の接続構造体の製造方法は、下記［１０］に示す方法であってよい。 The method for manufacturing the connection structure on the above side surface may be the method shown in the following [10].
［１０］前記第１の電極の高さと前記第２の電極の高さの合計が、前記はんだ粒子の平均粒子径よりも小さい、［９］に記載の接続構造体の製造方法。 [10] The method for manufacturing a connection structure according to [9], wherein the sum of the height of the first electrode and the height of the second electrode is smaller than the average particle diameter of the solder particles.
　本発明によれば、導電粒子（はんだ粒子）の充分な捕捉率を確保しつつ、隣り合う電極間の充分な絶縁性を確保することができる、回路接続用接着剤フィルムを提供することができる。 According to the present invention, it is possible to provide 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). ..
図１は、回路接続用接着剤フィルムの一実施形態を示す模式断面図である。FIG. 1 is a schematic cross-sectional view showing an embodiment of an adhesive film for circuit connection. 図２は、図１の回路接続用接着剤フィルムにおける導電粒子の配置例を示す模式平面図である。FIG. 2 is a schematic plan view showing an example of arrangement of conductive particles in the circuit connection adhesive film of FIG. 1. 図３は、図１の回路接続用接着剤フィルムにおける導電粒子の配置例を示す模式平面図である。FIG. 3 is a schematic plan view showing an example of arrangement of conductive particles in the circuit connection adhesive film of FIG. 図４は、図１の回路接続用接着剤フィルムの製造に用いられる基体の模式断面図である。FIG. 4 is a schematic cross-sectional view of a substrate used for manufacturing the circuit connection adhesive film of FIG. 図５は、図４の基体の凹部の断面形状の変形例を示す図である。FIG. 5 is a diagram showing a modified example of the cross-sectional shape of the recess of the substrate of FIG. 図６は、図４の基体の凹部にはんだ粒子が配置された状態を示す図である。FIG. 6 is a diagram showing a state in which solder particles are arranged in the recesses of the substrate of FIG. 図７は、図１の回路接続用接着剤フィルムの製造方法の一工程を示す模式断面図である。FIG. 7 is a schematic cross-sectional view showing one step of the method for manufacturing the adhesive film for circuit connection of FIG. 図８は、図１の回路接続用接着剤フィルムの製造方法の一工程を示す模式断面図である。FIG. 8 is a schematic cross-sectional view showing one step of the method for manufacturing the adhesive film for circuit connection of FIG. 図９は、接続構造体の一実施形態を示す模式断面図である。FIG. 9 is a schematic cross-sectional view showing an embodiment of the connection structure. 図１０は、接続構造体の製造方法の一実施形態を示す模式断面図である。FIG. 10 is a schematic cross-sectional view showing an embodiment of a method for manufacturing a connection structure.
　以下、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。なお、以下で例示する材料は、特に断らない限り、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。本明細書において、「（メタ）アクリレート」とは、アクリレート、及び、それに対応するメタクリレートの少なくとも一方を意味する。「（メタ）アクリロイル」等の他の類似の表現においても同様である。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. The content of 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. In the numerical range described stepwise in the present specification, 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. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. As used herein, 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".
＜回路接続用接着剤フィルム＞
　一実施形態の回路接続用接着剤フィルムは、熱硬化性の接着剤フィルムであり、導電粒子として、平均粒子径が１～３０μｍであり、粒子径のＣ．Ｖ．値が２０％以下であるはんだ粒子を含有する。ここで、回路接続用とは、回路部材の接続（例えば発光素子の実装）に用いられることを意味する。回路接続用接着剤フィルムは、異方導電性を有していてもよいし、異方導電性を有していなくてもよい。すなわち、回路接続用接着剤フィルムは、異方導電性の接着剤フィルムであっても、非異方導電性（例えば等方導電性）の接着剤フィルムであってもよい。なお、ここでいう「異方導電性」とは、加圧方向には導通し、非加圧方向では絶縁性を保つという意味である。以下、図１を用いて、一実施形態の回路接続用接着剤フィルムについて説明する。 <Adhesive film for circuit connection>
The circuit connection adhesive film of one embodiment is a thermosetting adhesive film, and has an average particle diameter of 1 to 30 μm as conductive particles, and has a particle diameter of C.I. V. Contains solder particles with a value of 20% or less. Here, 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. The term "anisotropic conductivity" as used herein means that the material conducts in the pressurized direction and maintains the insulating property in the non-pressurized direction. Hereinafter, the circuit connection adhesive film of one embodiment will be described with reference to FIG. 1.
　図１は、一実施形態の回路接続用接着剤フィルムの縦断面を模式的に示す図である。「縦断面」とは、回路接続用接着剤フィルムの主面に対して略直交する断面（厚さ方向の断面）を意味する。図１に示される回路接続用接着剤フィルム１０は、熱硬化性の接着剤フィルム１と、当該接着剤フィルム１中に配置されたはんだ粒子２とで構成されている。 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.
　接着剤フィルム１は、第１の接着剤層３と、当該第１の接着剤層３上に設けられた第２の接着剤層４と、を備える。第１の接着剤層３は、後述する回路接続用接着剤フィルム１０の製造方法においてはんだ粒子２が転写される層である。 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.
　はんだ粒子２は、第１の接着剤層３と第２の接着剤層４との境界Ｓの近傍に配置されており、隣り合うはんだ粒子２，２の離間部分に境界Ｓが位置している。図１では、はんだ粒子２の表面（第２の接着剤層４側の表面）が、第１の接着剤層３の表面から露出しているが、はんだ粒子２は、その全体が第１の接着剤層３中に埋め込まれていてもよい。 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. .. In FIG. 1, 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.
　回路接続用接着剤フィルム１０の縦断面において、隣り合うはんだ粒子同士は、互いに離隔した状態で横方向に並んでいる。換言すると、回路接続用接着剤フィルム１０は、その縦断面において、隣りに位置するはんだ粒子と離隔した状態のはんだ粒子２が横方向に列をなしている中央領域１０ａと、はんだ粒子２が実質的に存在しない表面側領域１０ｂ，１０ｃとによって構成されている。ここで、「横方向」とは回路接続用接着剤フィルムの主面と略平行な方向（図１における左右方向）を意味する。隣り合うはんだ粒子同士が互いに離隔した状態で横方向に並んでいることは、例えば、走査型電子顕微鏡等により回路接続用接着剤フィルムの縦断面を観察することにより確認することができる。 In the vertical cross section of the circuit connection adhesive film 10, adjacent solder particles are lined up in the horizontal direction while being separated from each other. In other words, in the vertical cross section of the circuit connection adhesive film 10, the central region 10a in which the solder particles 2 in a state of being separated from the adjacent solder particles are arranged in a horizontal direction, and the solder particles 2 are substantially the same. It is composed of surface- side regions 10b and 10c that do not exist. Here, 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.
　はんだ粒子２の表面から回路接続用接着剤フィルム１０の表面（第１の接着剤層３における第２の接着剤層４側とは反対側の面３ａ及び第２の接着剤層４における第１の接着剤層３側とは反対側の面４ａ）までの最短距離（図１中のｄ１１及びｄ２１）は、０．０５～１．５μｍであってよい。最短距離ｄ１１，ｄ２１が０．０５μｍ以上であると、圧着後に回路部材間に接着剤樹脂を良好に充填することができるため回路の絶縁性が向上する傾向があり、最短距離ｄ１１，ｄ２１が１．５μｍ以下であると、圧着時の導電粒子の流動が抑制され、高い粒子捕捉性が得られる傾向がある。最短距離ｄ１１，ｄ２１は、０．１μｍ以上又は０．２μｍ以上であってもよく、１．４μｍ以下又は１．２μｍ以下であってもよい。最短距離ｄ１１と最短距離ｄ２１とは、同一であっても異なっていてもよい。 From the surface of the solder particles 2 to the surface of the adhesive film 10 for circuit connection (the surface 3a of the first adhesive layer 3 opposite to the side of the second adhesive layer 4 and the first surface of the second adhesive layer 4). 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 μm. When the shortest distances d11 and d21 are 0.05 μm or more, 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. When it is 5.5 μm or less, the flow of conductive particles during crimping is suppressed, and high particle capture properties tend to be obtained. The shortest distances d11 and d21 may be 0.1 μm or more or 0.2 μm or more, and may be 1.4 μm or less or 1.2 μm or less. The shortest distance d11 and the shortest distance d21 may be the same or different.
　図２及び図３は、回路接続用接着剤フィルム１０におけるはんだ粒子２の配置例を模式的に示す平面図である。図２及び図３に示されるように、複数のはんだ粒子２の少なくとも一部は、回路接続用接着剤フィルムの平面視において、所定のパターンで並んでいてよい。図２では、はんだ粒子２が回路接続用接着剤フィルム１０の全体の領域に対して規則的且つほぼ均等の間隔で配置されているが、例えば、図３に示されるように、回路接続用接着剤フィルムの平面視において、複数のはんだ粒子２が規則的に配置されている領域１０ｄと、はんだ粒子２が実質的に存在しない領域１０ｅとが規則的に形成されるように、はんだ粒子２が配置されていてもよい。はんだ粒子２の位置及び個数は、例えば、接続すべき電極の形状、サイズ及びパターン等に応じて、設定することができる。複数のはんだ粒子の少なくとも一部が所定のパターンで並んでいることは、例えば、電子顕微鏡等を用いて、回路接続用接着剤フィルムの主面上方より該回路接続用接着剤フィルムを観察することにより確認することができる。 2 and 3 are plan views schematically showing an arrangement example of the solder particles 2 in the circuit connection adhesive film 10. As shown in FIGS. 2 and 3, at least a part of the plurality of solder particles 2 may be arranged in a predetermined pattern in a plan view of the circuit connection adhesive film. In FIG. 2, 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. In the plan view of the agent film, 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.
　はんだ粒子２が他のはんだ粒子２と離間した状態（単分散状態）で存在している比率（単分散率）は、好ましくは９０．０％以上であり、９３．０％以上、９５．０％以上、９７．０％以上又は９８．０％以上であってもよい。単分散率の上限値は１００％である。単分散率が高いほど、絶縁信頼性に優れる接続構造体が得られやすくなる。このような分散状態は、後述する回路接続用接着剤フィルム１０の製造方法において、はんだ粒子２が所定の配列で配置された基体を用いることによって形成することができる。 The ratio (single dispersion ratio) in which the solder particles 2 exist in a state of being separated from the other solder particles 2 (single dispersion state) 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.
　回路接続用接着剤フィルム１０は、はんだ粒子２の平均粒子径の１．０倍より大きく、１．５倍未満の厚さを有する。すなわち、はんだ粒子２の平均粒子径に対する回路接続用接着剤フィルム１０の厚さの比は１．０超１．５未満である。はんだ粒子２の平均粒子径に対する回路接続用接着剤フィルム１０の厚さの比は、対向する電極間でのはんだ粒子２の捕捉率がより向上し、隣り合う電極間の絶縁抵抗がより向上する観点から、１．４以下、１．３以下、１．２以下又は１．１以下であってよい。すなわち、はんだ粒子２の平均粒子径に対する回路接続用接着剤フィルム１０の厚さの比は、１．０超１．４以下、１．０超１．３以下、１．０超１．２以下又は１．０超１．１以下であってよい。なお、回路接続用接着剤フィルム１０の厚さは、接着剤フィルム１の厚さに等しい。 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. That is, 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.
　回路接続用接着剤フィルム１０の厚さは、例えば、２．０μｍ以上、３．０μｍ以上又は４．０μｍ以上であってよく、１０．０μｍ以下、８．０μｍ以下又は６．０μｍ以下であってよく、２．０～１０．０μｍ、３．０～８．０μｍ又は４．０～６．０μｍであってよい。 The thickness of the circuit connection adhesive film 10 may be, for example, 2.0 μm or more, 3.0 μm or more, or 4.0 μm or more, and may be 10.0 μm or less, 8.0 μm or less, or 6.0 μm or less. It may be 2.0 to 10.0 μm, 3.0 to 8.0 μm or 4.0 to 6.0 μm.
　回路接続用接着剤フィルム１０は、はんだ粒子の融点をＴｍ℃とすると、窒素雰囲気下、１０℃／分の昇温速度で加熱したときのＴｍ℃での硬化率が８０％以上である。一般的に、はんだ粒子を用いた接続構造体の製造においては、はんだを溶融させて回路部材同士を接続させた後に封止樹脂を硬化させる。そのため、通常は、はんだ粒子の融点は接着剤成分の硬化温度よりも低い。しかし、回路接続用接着剤フィルム１０の厚さが導電粒子の平均粒子径の１．５倍未満であると、導電粒子の量に対して接着剤成分の量が少なくなるため、導電粒子としてはんだ粒子を用いた場合には、接続時の熱圧着によって接着剤フィルム１中に拡散したはんだによって絶縁性が低下する（例えばショートが生じやすくなる）ことがある。一方、上記の硬化性を有する回路接続用接着剤フィルム１０では、接続時の熱圧着によりはんだ粒子２が溶融する前に接着剤フィルム１が硬化し、はんだの拡散が抑制されるため、回路接続用接着剤フィルム１０の厚さが導電粒子の平均粒子径の１．５倍未満であっても、隣り合う電極間の充分な絶縁性が確保される。上記条件でのＴｍ℃での硬化率は、隣り合う電極間の絶縁性がより良好となる観点から、８５％以上、９０％以上又は９５％以上であってもよく、１００％であってもよい。 Assuming that the melting point of the solder particles is T m ° C, 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. .. Generally, in the manufacture of a connection structure using solder particles, the solder is melted to connect the circuit members to each other, and then the sealing resin is cured. Therefore, the melting point of the solder particles is usually lower than the curing temperature of the adhesive component. However, if 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. When particles are used, 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. On the other hand, in the above-mentioned curable adhesive film 10 for circuit 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.
　上記回路接続用接着剤フィルム１０の硬化率（窒素雰囲気下、１０℃／分の昇温速度で加熱したときのＴｍ℃での硬化率）は、示差走査熱量計（Ｄｉｆｆｅｒｅｎｔｉａｌ　Ｓｃａｎｎｉｎｇ　Ｃａｌｏｒｉｍｅｔｅｒ）を用いて測定される発熱量を用いて求めることができる。具体的には、示差走査熱量計を用いて、窒素（Ｎ２）雰囲気下、１０℃／分の昇温速度で回路接続用接着剤フィルム１０の発熱量を測定し、５０℃から回路接続用接着剤フィルム１０が完全に硬化するまでの発熱量（Ｑ１）と、５０℃からはんだ粒子の融点Ｔｍ℃までの発熱量（Ｑ２）とを求めた後、求めた値を下記式（Ａ）に代入することで硬化率を算出することができる。Ｑ１を求める際には、測定で得られたＤＳＣ曲線の微分曲線（ＤＤＳＣ曲線）の変化率が０．０１［Ｗ・ｇ℃］以下となった場合に回路接続用接着剤フィルム１０が完全に硬化したと判断する。
硬化率（％）＝Ｑ２／Ｑ１×１００　　（Ａ） 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. of the solder particles, the calculated values are calculated by the following formula (Q 2). The curing rate can be calculated by substituting into A). When determining Q1 , 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)
　上記硬化率を有する回路接続用接着剤フィルム１０は、例えば、環状エーテル基を有する化合物等を熱硬化性成分として用いること、重合開始剤の種類の選択、配合量の調整などによって、当業者であれば容易に作製することができる。 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.
　上述した特徴を備える回路接続用接着剤フィルム１０は、第１の電極を有する第１の回路部材と第２の電極を有する第２の回路部材とを接着すると共に、第１の電極と第２の電極とを互いに電気的に接続する用途に好適に用いられる。特に、回路接続用接着剤フィルム１０は、導電粒子としてはんだ粒子を含有し、且つ、厚さがはんだ粒子２の平均粒子径の１．０倍より大きく、１．５倍未満であることから、低圧（例えば第１の回路部材又は第２の回路部材のうち、接着面積が小さい方の回路部材の面積を基準として、５ＭＰａ以下）での実装に好適に用いられる。 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. In particular, 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).
　回路接続用接着剤フィルム１０によれば、導電粒子（はんだ粒子）の充分な捕捉率を確保しつつ、隣り合う電極間の充分な絶縁性を確保することができる。特に、接続される電極の高さの合計値（第１の電極の高さと第２の電極の高さの合計値）が、はんだ粒子の平均粒子径よりも小さい場合において、上記効果が顕著となる。また、回路接続用接着剤フィルム１０によれば、充分に低い接続抵抗が得られる傾向がある。 According to 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). In particular, 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.
　以下、接着剤フィルム１及びはんだ粒子２の詳細について説明する。 Hereinafter, the details of the adhesive film 1 and the solder particles 2 will be described.
（接着剤フィルム）
　接着剤フィルム１は、例えば、導電性を有しない材料（絶縁性樹脂等）で構成される絶縁性の接着剤フィルムである。接着剤フィルム１を構成する第１の接着剤層３及び第２の接着剤層４は、それぞれ、熱硬化性の接着剤組成物で構成されている。以下では、場合により、第１の接着剤層３を構成する接着剤組成物を「第１の接着剤組成物」といい、第２の接着剤層４を構成する接着剤組成物を「第２の接着剤組成物」という。 (Adhesive film)
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. Hereinafter, the adhesive composition constituting the first adhesive layer 3 may be referred to as a “first adhesive composition”, and the adhesive composition constituting the second adhesive layer 4 may be referred to as a “first adhesive composition”. 2 adhesive composition ".
　接着剤組成物（第１の接着剤組成物及び第２の接着剤組成物）は、熱硬化性成分を少なくとも含む。熱硬化性成分は、接続時に流動可能であり、加熱によって硬化する成分である。接着剤組成物は、熱硬化性成分として、重合性化合物及び熱重合開始剤を含んでいてよい。接続抵抗の低減効果により優れる観点では、重合性化合物がカチオン重合性化合物であり、熱重合開始剤が熱カチオン重合開始剤であってよい。 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. From the viewpoint of being more excellent in the effect of reducing the connection resistance, the polymerizable compound may be a cationically polymerizable compound, and the thermal polymerization initiator may be a thermal cationic polymerization initiator.
［カチオン重合性化合物］
　カチオン重合性化合物としては、接続抵抗の低減効果が更に向上し、接続信頼性により優れる観点から、環状エーテル基を有する化合物であってよい。環状エーテル基を有する化合物の中でも、脂環式エポキシ化合物及びオキセタン化合物からなる群より選ばれる少なくとも１種を用いる場合、接続抵抗の低減効果が一層向上する傾向がある。カチオン重合性化合物は、所望の溶融粘度が得られ易い観点から、脂環式エポキシ化合物及びオキセタン化合物の両方を含んでいてよい。 [Cation-polymerizable compound]
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. Among 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.
　脂環式エポキシ化合物は、脂環式エポキシ基（例えば、エポキシシクロヘキシル基）を有する化合物であれば特に制限なく使用することができる。脂環式エポキシ化合物の市販品としては、セロキサイド８０１０（商品名、ビ－７－オキサビシクロ［４．１．０］ヘプタン、株式会社ダイセル製）の他、例えば、ＥＨＰＥ３１５０、ＥＨＰＥ３１５０ＣＥ、セロキサイド２０２１Ｐ、セロキサイド２０８１（商品名、株式会社ダイセル製）等が挙げられる。これらは、１種の化合物を単独で用いてもよく、複数種を組み合わせて用いてもよい。 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.
　オキセタン化合物は、オキセタニル基を有する化合物であれば特に制限なく使用することができる。オキセタン化合物の市販品としては、例えば、ＥＴＥＲＮＡＣＯＬＬ　ＯＸＢＰ（商品名、４，４’－ビス［（３－エチル－３－オキセタニル）メトキシメチル］ビフェニル、宇部興産株式会社製）、ＯＸＳＱ、ＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸＴ－１０１、ＯＸＴ－２１２（商品名、東亜合成株式会社製）等が挙げられる。これらは、１種の化合物を単独で用いてもよく、複数種を組み合わせて用いてもよい。 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.
　環状エーテル基を有する化合物としては、脂環式エポキシ化合物以外のエポキシ化合物を用いてもよい。具体的には、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等の芳香族系炭化水素基を有するエポキシ化合物（例えば、三菱化学株式会社製の商品名「ｊＥＲ１０１０」等）を用いることもできる。芳香族系炭化水素基を有するエポキシ化合物は、接続抵抗の低減効果が更に向上し、接続信頼性により優れる観点から、脂環式エポキシ化合物と組み合わせて用いてよい。 As the compound having a cyclic ether group, an epoxy compound other than the alicyclic epoxy compound may be used. Specifically, for example, 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. can. 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.
［熱カチオン重合開始剤］
　熱カチオン重合開始剤は、例えば、加熱により酸等を発生して重合を開始させることができる化合物（熱潜在性カチオン発生剤）である。熱カチオン重合開始剤はカチオンとアニオンとから構成される塩化合物であってよい。熱カチオン重合開始剤は、例えば、ＢＦ４ －、ＢＲ４ －（Ｒは、２以上のフッ素原子又は２以上のトリフルオロメチル基で置換されたフェニル基を示す。）、ＰＦ６ －、ＳｂＦ６ －、ＡｓＦ６ －等のアニオンを有する、スルホニウム塩、ホスホニウム塩、アンモニウム塩、ジアゾニウム塩、ヨードニウム塩、アニリニウム塩、ピリジニウム塩等のオニウム塩などが挙げられる。これらは、１種を単独で用いてもよく、複数種を組み合わせて用いてもよい。 [Thermal cationic polymerization initiator]
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.
　熱カチオン重合開始剤は、速硬化性の観点から、例えば、構成元素としてホウ素を含むアニオンを有する塩化合物であってよい。このような塩化合物としては、例えば、ＢＦ４ －又はＢＲ４ －（Ｒは、２以上のフッ素原子又は２以上のトリフルオロメチル基で置換されたフェニル基を示す。）を有する塩化合物が挙げられる。構成元素としてホウ素を含むアニオンは、ＢＲ４ －であってよく、より具体的には、テトラキス（ペンタフルオロフェニル）ボレートであってもよい。 From the viewpoint of quick curing, the thermal cationic polymerization initiator may be, for example, a salt compound having an anion containing boron as a constituent element. Examples of such 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.
　熱カチオン重合開始剤は、保存安定性の観点から、下記式（Ｉ）又は下記式（ＩＩ）で表されるカチオンを有する塩化合物であってよい。
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
 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.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
　式（Ｉ）中、Ｒ１及びＲ２は、それぞれ独立して、水素原子、炭素数１～２０のアルキル基又は置換基を有する若しくは無置換の芳香族系炭化水素基を含む有機基を示し、Ｒ３は、炭素数１～６のアルキル基を示す。 In formula (I), 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.
　式（Ｉ）で表されるカチオンを有する塩化合物は、保存安定性と低温活性の両立観点から、芳香族スルホニウム塩化合物（芳香族スルホニウム塩型熱酸発生剤）であってよい。すなわち、式（Ｉ）におけるＲ１及びＲ２の少なくとも一方が置換基を有する若しくは無置換の芳香族系炭化水素基を含む有機基であってよい。式（Ｉ）で表されるカチオンを有する塩化合物におけるアニオンは、構成元素としてアンチモンを含むアニオンであってよく、例えば、ヘキサフルオロアンチモネート（ヘキサフルオロアンチモン酸）であってよい。 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).
　式（Ｉ）で表されるカチオンを有する化合物の具体例としては、１－ナフチルメチル－ｐ－ヒドロキシフェニルスルホニウムヘキサフルオロアンチモネート（三新化学株式会社製、ＳＩ－６０主剤）等が挙げられる。 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).
　式（ＩＩ）中、Ｒ４及びＲ５は、それぞれ独立して、水素原子、炭素数１～２０のアルキル基又は置換基を有する若しくは無置換の芳香族系炭化水素基を含む有機基を示し、Ｒ６及びＲ７は、それぞれ独立して、炭素数１～６のアルキル基を示す。 In formula (II), 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.
　式（ＩＩ）で表されるカチオンを有する塩化合物（第４級アンモニウム塩型熱酸発生剤）は、カチオン硬化に対する硬化阻害を起こし得る物質に対する耐性を有することから、例えば、アニリニウム塩化合物であってよい。すなわち、式（ＩＩ）におけるＲ４及びＲ５の少なくとも一方が置換基を有する若しくは無置換の芳香族系炭化水素基を含む有機基であってよい。アニリニウム塩化合物としては、例えば、Ｎ，Ｎ－ジメチルアニリニウム塩、Ｎ，Ｎ－ジエチルアニリニウム塩等のＮ，Ｎ－ジアルキルアニリニウム塩などが挙げられる。式（ＩＩ）で表されるカチオンを有する塩化合物におけるアニオンは、構成元素としてホウ素を含むアニオンであってよく、例えば、テトラキス（ペンタフルオロフェニル）ボレートであってよい。 The salt compound having a cation represented by the formula (II) (quaternary ammonium salt type thermoacid generator) 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. Examples of 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.
　式（ＩＩ）で表されるカチオンを有する化合物は、構成元素としてホウ素を含むアニオンを有するアニリニウム塩であってよい。このような塩化合物の市販品としては、例えば、ＣＸＣ－１８２１（商品名、Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製）等が挙げられる。 The compound having a cation represented by the formula (II) may be an anilinium salt having an anion containing boron as a constituent element. Examples of commercially available products of such salt compounds include CXC-1821 (trade name, manufactured by King Industries) and the like.
　熱カチオン重合開始剤の含有量は、接着剤フィルムの形成性及び硬化性を担保する観点から、カチオン重合性化合物１００質量部に対して、例えば、０．１～２０質量部、１～１８質量部、３～１５質量部又は５～１２質量部であってよい。なお、第１の接着剤組成物中の熱カチオン重合開始剤の含有量（第１の接着剤組成物中のカチオン重合性化合物１００質量部基準）が上記範囲であってよく、第２の接着剤組成物中の熱カチオン重合開始剤の含有量（第２の接着剤組成物中のカチオン重合性化合物１００質量部基準）が上記範囲であってもよい。 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.
　熱硬化性成分の含有量（例えば重合性化合物と熱重合開始剤の合計含有量）は、接着剤フィルムの硬化性を担保する観点から、接着剤組成物の全質量を基準として、例えば、５質量％以上、１０質量％以上、１５質量％以上又は２０質量％以上であってよい。熱硬化性成分の含有量は、接着剤フィルムの形成性を担保する観点から、接着剤組成物の全質量を基準として、例えば、７０質量％以下、６０質量％以下、５０質量％以下又は４０質量％以下であってよい。これらの観点から、熱硬化性成分の含有量は、接着剤組成物の全質量を基準として、例えば、５～７０質量％、１０～６０質量％、１５～５０質量％又は２０～４０質量％であってよい。なお、第１の接着剤組成物中の熱硬化性成分の含有量（第１の接着剤組成物の全質量基準）が上記範囲であってよく、第２の接着剤組成物中の熱硬化性成分の含有量（第２の接着剤組成物の全質量基準）が上記範囲であってよい。以下同様に、接着剤組成物に含まれる各成分の含有量（接着剤組成物の全質量基準）は、第１の接着剤組成物中の熱硬化性成分の含有量（第１の接着剤組成物の全質量基準）と言い換えることができ、第２の接着剤組成物中の熱硬化性成分の含有量（第２の接着剤組成物の全質量基準）と言い換えることもできる。 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. From these viewpoints, 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. Similarly, the content of each component contained in the adhesive composition (based on the total mass of 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).
［その他の成分］
　接着剤組成物（第１の接着剤組成物及び第２の接着剤組成物）は、熱硬化性成分以外に、例えば、熱可塑性樹脂、充填材、カップリング剤等を更に含んでいてよい。 [Other ingredients]
The adhesive composition (first adhesive composition and second adhesive composition) may further contain, for example, a thermoplastic resin, a filler, a coupling agent, or the like, in addition to the thermosetting component.
　熱可塑性樹脂は、接着剤フィルムのフィルム形成性の向上に寄与する。熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、アクリルゴム、エポキシ樹脂（２５℃で固形）等が挙げられる。上記フェノキシ樹脂としては、例えば、フルオレン型フェノキシ樹脂、ビスフェノールＡ・ビスフェノールＦ共重合型フェノキシ樹脂等が挙げられる。これらは、１種を単独で用いてもよく、複数種を組み合わせて用いてもよい。 The thermoplastic resin contributes to the improvement of the film formability of the adhesive film. Examples of the 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. Examples of the 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.
　熱可塑性樹脂の重量平均分子量（Ｍｗ）は、実装時の樹脂排除性の観点から、例えば、５０００～２０００００、１００００～１０００００、２００００～８００００又は４００００～６００００であってよい。なお、Ｍｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、標準ポリスチレンによる検量線を用いて換算した値を意味する。 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. In addition, Mw means a value measured by gel permeation chromatography (GPC) and converted using the calibration curve by standard polystyrene.
　熱可塑性樹脂の含有量は、接着剤組成物の全質量を基準として、例えば、１質量％以上、５質量％以上、１０質量％以上又は２０質量％以上であってよく、７０質量％以下、６０質量％以下、５０質量％以下又は４０質量％以下であってよく、１～７０質量％、５～６０質量％、１０～５０質量％又は２０～４０質量％であってよい。 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.
　充填材としては、例えば、非導電性のフィラー（例えば、非導電粒子）が挙げられる。充填材は、無機フィラー及び有機フィラーのいずれであってもよい。無機フィラーとしては、例えば、シリカ微粒子、アルミナ微粒子、シリカ－アルミナ微粒子、チタニア微粒子、ジルコニア微粒子等の金属酸化物微粒子；金属窒化物微粒子などの無機微粒子が挙げられる。有機フィラーとしては、例えば、シリコーン微粒子、メタアクリレート・ブタジエン・スチレン微粒子、アクリル・シリコーン微粒子、ポリアミド微粒子、ポリイミド微粒子等の有機微粒子が挙げられる。これらは、１種を単独で用いてもよく、複数種を組み合わせて用いてもよい。充填材は、例えば、シリカ微粒子であってよい。充填材の含有量は、接着剤組成物の全質量を基準として、例えば、０．１～１０質量％であってよい。 Examples of the filler include non-conductive fillers (for example, non-conductive particles). The filler may be either an inorganic filler or an organic filler. Examples of 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. Examples of 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.
　カップリング剤としては、例えば、（メタ）アクリロイル基、メルカプト基、アミノ基、イミダゾール基、エポキシ基等の有機官能基を有するシランカップリング剤（γ―グリシドキシプロピルトリメトキシシラン等）、テトラアルコキシシラン等のシラン化合物、テトラアルコキシチタネート誘導体、ポリジアルキルチタネート誘導体などが挙げられる。これらは、１種を単独で用いてもよく、複数種を組み合わせて用いてもよい。接着剤組成物がカップリング剤を含有することによって、接着性を更に向上させることができる。カップリング剤の含有量は、接着剤組成物の全質量を基準として、例えば、０．１～１０質量％であってよい。 Examples of the coupling agent 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 (γ-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. When 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.
　接着剤組成物（第１の接着剤組成物及び第２の接着剤組成物）は、その他の成分として、軟化剤、促進剤、劣化防止剤、着色剤、難燃化剤、チキソトロピック剤等のその他の添加剤を更に含んでいてもよい。その他の添加剤の含有量は、接着剤組成物の全質量を基準として、例えば、０．１～１０質量％であってよい。 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.
　第１の接着剤組成物と第２の接着剤組成物は、互いに同一の成分を含んでいてよく、異なる成分を含んでいてもよい。 The first adhesive composition and the second adhesive composition may contain the same components as each other, or may contain different components.
　第１の接着剤層３の厚さｄ１（図１中のｄ１で示す距離）は、回路接続用接着剤フィルム１０の製造時におけるはんだ粒子２の転写性の観点から、例えば、０．５μｍ以上、１．０μｍ以上又は２．０μｍ以上であってよい。第１の接着剤層３の厚さｄ１は、接続時にはんだ粒子をより一層効率的に捕捉することができる観点から、例えば、５．０μｍ以下、４．０μｍ以下又は３．０μｍ以下であってよい。これらの観点から、第１の接着剤層３の厚さｄ１は、例えば、０．５～５．０μｍ、１．０～４．０μｍ又は２．０～３．０μｍであってよい。 The thickness d1 (distance indicated by d1 in FIG. 1) of the first adhesive layer 3 is, for example, 0.5 μm 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 μm or more or 2.0 μm or more. The thickness d1 of the first adhesive layer 3 is, for example, 5.0 μm or less, 4.0 μm or less, or 3.0 μm 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 μm, 1.0 to 4.0 μm, or 2.0 to 3.0 μm.
　第２の接着剤層４の厚さｄ２（図１中のｄ２で示す距離）は、接続する回路部材の電極の高さ等に応じて適宜設定してよい。第２の接着剤層４の厚さｄ２は、電極間のスペースを充分に充填して電極を封止することができ、より良好な接続信頼性が得られる観点から、例えば、０．５μｍ以上、１．０μｍ以上又は２．０μｍ以上であってよく、１０μｍ以下、５．０μｍ以下、４．０μｍ以下又は３．０μｍ以下であってよく、０．５～１０μｍ、０．５～５．０μｍ、１．０～４．０μｍ又は２．０～３．０μｍであってよい。 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 μm or more. , 1.0 μm or more or 2.0 μm or more, 10 μm or less, 5.0 μm or less, 4.0 μm or less or 3.0 μm or less, 0.5 to 10 μm, 0.5 to 5.0 μm , 1.0 to 4.0 μm or 2.0 to 3.0 μm.
　第１の接着剤層３の厚さｄ１及び第２の接着剤層の厚さｄ２は、例えば、回路接続用接着剤フィルム１０を２枚のガラス（厚さ：１ｍｍ程度）で挟み込み、ビスフェノールＡ型エポキシ樹脂（商品名：ｊＥＲ８１１、三菱ケミカル株式会社製）１００ｇと、硬化剤（商品名：エポマウント硬化剤、リファインテック株式会社製）１０ｇとからなる樹脂組成物で注型後に、研磨機を用いて断面研磨を行い、走査型電子顕微鏡（ＳＥＭ、商品名：ＳＥ－８０２０、株式会社日立ハイテクサイエンス製）を用いて測定することによって求めることができる。 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. After casting with 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.).
（はんだ粒子）
　はんだ粒子は、例えば、接続温度よりも低い融点を有する。そのため、はんだ粒子は、接続時の熱圧着により溶融し電極上に固着する。これにより、対向する電極同士が電気的に接続される。はんだ粒子の融点は、低温での実装が可能となる観点から、例えば、２８０℃以下、２２０℃以下、１８０℃以下、１６０℃以下又は１４０℃以下であってよい。はんだ粒子の融点は、例えば、１００℃以上である。 (Solder particles)
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.
　はんだ粒子は、接続強度と低融点の両立の観点から、スズ、スズ合金、インジウム及びインジウム合金からなる群より選択される少なくとも一種を含んでいてよい。 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.
　スズ合金としては、例えば、Ｉｎ－Ｓｎ合金、Ｉｎ－Ｓｎ－Ａｇ合金、Ｓｎ－Ａｕ合金、Ｓｎ－Ｂｉ合金、Ｓｎ－Ｂｉ－Ａｇ合金、Ｓｎ－Ａｇ－Ｃｕ合金、Ｓｎ－Ｃｕ合金等を用いることができる。これらのスズ合金の具体例としては、下記の例が挙げられる。
・Ｉｎ－Ｓｎ（Ｉｎ５２質量％、Ｓｎ４８質量％　融点１１８℃）
・Ｉｎ－Ｓｎ－Ａｇ（Ｉｎ２０質量％、Ｓｎ７７．２質量％、Ａｇ２．８質量％　融点１７５℃）
・Ｓｎ－Ｂｉ（Ｓｎ４３質量％、Ｂｉ５７質量％　融点１３８℃）
・Ｓｎ－Ｂｉ－Ａｇ（Ｓｎ４２質量％、Ｂｉ５７質量％、Ａｇ１質量％　融点１３９℃）・Ｓｎ－Ａｇ－Ｃｕ（Ｓｎ９６．５質量％、Ａｇ３質量％、Ｃｕ０．５質量％　融点２１７℃）
・Ｓｎ－Ｃｕ（Ｓｎ９９．３質量％、Ｃｕ０．７質量％　融点２２７℃）
・Ｓｎ－Ａｕ（Ｓｎ２１．０質量％、Ａｕ７９．０質量％　融点２７８℃） As the 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.
-In-Sn (In 52% by mass, Sn 48% by mass, melting point 118 ° C)
In-Sn-Ag (In 20% by mass, Sn77.2% by mass, Ag 2.8% by mass, melting point 175 ° C.)
-Sn-Bi (Sn43% by mass, Bi57% by mass, melting point 138 ° C.)
-Sn-Bi-Ag (Sn42% by mass, Bi57% by mass, Ag1% by mass, melting point 139 ° C.)-Sn-Ag-Cu (Sn96.5% by mass, Ag3% by mass, Cu0.5% by mass, melting point 217 ° C.)
-Sn-Cu (Sn99.3% by mass, Cu0.7% by mass, melting point 227 ° C)
-Sn-Au (Sn21.0% by mass, Au79.0% by mass, melting point 278 ° C.)
　インジウム合金としては、例えば、Ｉｎ－Ｂｉ合金、Ｉｎ－Ａｇ合金等を用いることができる。これらのインジウム合金の具体例としては、下記の例が挙げられる。
・Ｉｎ－Ｂｉ（Ｉｎ６６．３質量％、Ｂｉ３３．７質量％　融点７２℃）
・Ｉｎ－Ｂｉ（Ｉｎ３３．０質量％、Ｂｉ６７．０質量％　融点１０９℃）
・Ｉｎ－Ａｇ（Ｉｎ９７．０質量％、Ａｇ３．０質量％　融点１４５℃）
　なお、上述したスズを含むインジウム合金は、スズ合金に分類されるものとする。 As 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.
　はんだ粒子は、高温高湿試験時及び熱衝撃試験時により高い信頼性が得られる観点から、Ｉｎ－Ｂｉ合金、Ｉｎ－Ｓｎ合金、Ｉｎ－Ｓｎ－Ａｇ合金、Ｓｎ－Ａｕ合金、Ｓｎ－Ｂｉ合金、Ｓｎ－Ｂｉ－Ａｇ合金、Ｓｎ－Ａｇ－Ｃｕ合金及びＳｎ－Ｃｕ合金からなる群より選択される少なくとも一種を含んでよい。 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.
　上記スズ合金又はインジウム合金は、はんだ粒子の用途（使用時の温度）等に応じて選択してもよい。例えば、低温での融着にはんだ粒子を用いる場合、Ｉｎ－Ｓｎ合金、Ｓｎ－Ｂｉ合金を採用すれば、１５０℃以下で融着させることができる。Ｓｎ－Ａｇ－Ｃｕ合金、Ｓｎ－Ｃｕ合金等の融点の高い材料を採用した場合、高温放置後においても高い信頼性を維持することができる。 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.
　はんだ粒子は、Ａｇ、Ｃｕ、Ｎｉ、Ｂｉ、Ｚｎ、Ｐｄ、Ｐｂ、Ａｕ、Ｐ及びＢから選ばれる一種以上を含んでもよい。はんだ粒子がＡｇ又はＣｕを含む場合、はんだ粒子の融点を２２０℃程度まで低下させることができ、且つ、電極との接合強度がより向上するため、より良好な導通信頼性が得られ易くなる。 The solder particles may contain one or more selected from Ag, Cu, Ni, Bi, Zn, Pd, Pb, Au, P and B. When the solder particles contain Ag or Cu, 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.
　はんだ粒子のＣｕ含有率は、例えば０．０５～１０質量％であり、０．１～５質量％又は０．２～３質量％であってもよい。Ｃｕ含有率が０．０５質量％以上であると、より良好なはんだ接続信頼性を達成し易くなる。また、Ｃｕ含有率が１０質量％以下であると、融点が低く、濡れ性に優れたはんだ粒子となり易く、結果としてはんだ粒子による接合部の接続信頼性が良好となり易い。 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. When the Cu content is 0.05% by mass or more, it becomes easy to achieve better solder connection reliability. Further, when 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.
　はんだ粒子のＡｇ含有率は、例えば０．０５～１０質量％であり、０．１～５質量％又は０．２～３質量％であってもよい。Ａｇ含有率が０．０５質量％以上であると、より良好なはんだ接続信頼性を達成し易くなる。また、Ａｇ含有率が１０質量％以下であると、融点が低く、濡れ性に優れたはんだ粒子となり易く、結果としてはんだ粒子による接合部の接続信頼性が良好となり易い。 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. When the Ag content is 0.05% by mass or more, it becomes easy to achieve better solder connection reliability. Further, when 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.
　はんだ粒子は、表面の一部に平面部を有してよい。このようなはんだ粒子を用いる場合、はんだ粒子が有する平面部が電極と接することで、当該平面部と電極との間で広い接触面積を確保することができる。また、はんだが濡れ広がり易い材料から形成された電極と、はんだが濡れ広がり難い材料から形成された電極とを接続する際に、後者の電極側にはんだ粒子の平面部が配置されるように調整することで、両電極間の接続を好適に行うことができる。はんだ粒子における上記平面部以外の表面は、球冠状であってよい。すなわち、はんだ粒子は、平面部と、球冠状の曲面部と、を有するものであってよい。具体的には、はんだ粒子は、直径Ａを有する球の表面の一部に直径Ｂの平面部が形成された形状を有していてよい。このようなはんだ粒子を用いる場合、より優れた導通信頼性と絶縁信頼性が得られやすい。 The solder particles may have a flat surface on a part of the surface. When such solder particles are used, 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. Further, when connecting an electrode made of a material in which solder easily wets and spreads and an electrode made of a material in which solder does not easily wet and spread, 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. That is, the solder particles may have a flat surface portion and a spherical crown-shaped curved surface portion. Specifically, 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. When such solder particles are used, more excellent conduction reliability and insulation reliability can be easily obtained.
　はんだ粒子が直径Ａを有する球の表面の一部に直径Ｂの平面部が形成された形状を有する場合、より優れた導通信頼性及び絶縁信頼性を実現する観点から、はんだ粒子の直径Ａに対する平面部の直径Ｂの比（Ｂ／Ａ）は、例えば０．０１超１．０未満（０．０１＜Ｂ／Ａ＜１．０）であってよく、０．１～０．９であってもよい。はんだ粒子の直径Ａ及び平面部の直径Ｂは、例えば走査型電子顕微鏡等により観察することができる。具体的には、任意のはんだ粒子を走査型電子顕微鏡により観察し、画像を撮影する。得られた画像からはんだ粒子の直径Ａ及び平面部の直径Ｂを測定し、その粒子のＢ／Ａを求める。この作業を３００個のはんだ粒子に対して行って平均値を算出し、はんだ粒子のＢ／Ａとする。 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. From the obtained image, 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.
　はんだ粒子の投影像に外接する四角形を二対の平行線により作成した場合において、対向する辺間の距離をそれぞれＸ及びＹ（但しＹ＜Ｘ）とすると、Ｘに対するＹの比（Ｙ／Ｘ）は、０．８超１．０以下（０．８＜Ｙ／Ｘ≦１．０）であってよく、０．８超１．０未満又は０．８１～０．９９であってもよい。このようなはんだ粒子はより真球に近い粒子ということができる。はんだ粒子が真球に近い形状を有すると、後述する製造方法においてはんだ粒子を基体の凹部に収容し易い傾向がある。また、はんだ粒子が真球に近い形状を有することで、対向する複数の電極間をはんだ層を介して電気的に接続させるときに、はんだ粒子と電極との接触にムラが生じ難く、安定した接続が得られる傾向がある。はんだ粒子の投影像は、例えば、任意のはんだ粒子を走査型電子顕微鏡により観察して得ることができる。Ｙ／Ｘを求める際は、得られた投影像に対し二対の平行線を描画し、一対の平行線は平行線の距離が最小となる位置に、もう一対の平行線は平行線の距離が最大となる位置に配する。この作業を３００個のはんだ粒子に対して行ってＹ／Ｘの平均値を算出し、これをはんだ粒子のＹ／Ｘとする。 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. In addition, since the 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. When calculating 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.
　はんだ粒子の平均粒子径は１～３０μｍである。はんだ粒子の平均粒子径は、優れた導電性が得られやすい観点から、２μｍ以上又は４μｍ以上であってもよい。はんだ粒子の平均粒子径は、微小サイズの電極へのより良好な接続信頼性が得られやすい観点から、２５μｍ以下又は２０μｍ以下であってもよい。これらの観点から、はんだ粒子の平均粒子径は、２～２５μｍ又は４～２０μｍであってもよい。 The average particle size of the solder particles is 1 to 30 μm. The average particle size of the solder particles may be 2 μm or more or 4 μm or more from the viewpoint that excellent conductivity can be easily obtained. The average particle size of the solder particles may be 25 μm or less or 20 μm 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 μm or 4 to 20 μm.
　はんだ粒子の平均粒子径は、サイズに合わせた各種方法を用いて測定することができる。例えば、動的光散乱法、レーザ回折法、遠心沈降法、電気的検知帯法、共振式質量測定法等の方法を利用できる。さらに、光学顕微鏡、電子顕微鏡等によって得られる画像から、粒子サイズを測定する方法を利用できる。具体的な装置としては、フロー式粒子像分析装置、マイクロトラック、コールターカウンター等が挙げられる。なお、真球形ではないはんだ粒子の粒子径は、ＳＥＭの画像におけるはんだ粒子に外接する円の直径であってよい。 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.
　はんだ粒子の粒子径のＣ．Ｖ．値は、２０％以下である。粒子径のＣ．Ｖ．値は、はんだ粒子の粒子径の標準偏差を平均粒子径で割った値に１００を掛けることで算出される値であり、はんだ粒子の粒子径のばらつきの程度を示すパラメータである。はんだ粒子の粒子径のＣ．Ｖ．値が小さいことは、はんだ粒子の粒子径のばらつきが少ないことを意味する。はんだ粒子の粒子径の標準偏差は、上述したはんだ粒子の平均粒子径の測定方法と同じ方法で測定することができる。はんだ粒子の粒子径のＣ．Ｖ．値は、より優れた導電信頼性及び絶縁信頼性を実現できる観点から、１０％以下、９％以下、８％以下、７％以下又は５％以下であってもよい。はんだ粒子の粒子径のＣ．Ｖ．値の下限は特に限定されず、例えば、０．１％以上、１％以上又は２％以上であってもよい。すなわち、はんだ粒子の粒子径のＣ．Ｖ．値は、０．１～２０％、１～１０％、２～９％、２～８％等であってよい。 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. C. of the particle diameter of the solder particles. V. 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. C. of the particle diameter of the solder particles. 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.
　はんだ粒子の含有量は、導電性をより向上させることができる観点から、回路接続用接着剤フィルムの全質量を基準として、例えば、４０質量％以上、５０質量％以上又は６０質量％以上であってよい。はんだ粒子の含有量は、短絡を抑制し易い観点から、回路接続用接着剤フィルムの全質量を基準として、例えば、８０質量％以下、７５質量％以下又は７０質量％以下であってよい。これらの観点から、はんだ粒子の含有量は、回路接続用接着剤フィルムの全質量を基準として、例えば、４０～８０質量％、５０～７５質量％又は６０～７０質量％であってよい。 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.
　回路接続用接着剤フィルム１０におけるはんだ粒子の粒子密度は、安定した接続抵抗が得られる観点から、１００個／ｍｍ２以上、１０００個／ｍｍ２以上、３０００個／ｍｍ２以上又は５０００個／ｍｍ２以上であってよい。回路接続用接着剤フィルム１０におけるはんだ粒子の粒子密度は、隣り合う電極間の絶縁性を向上する観点から、１０００００個／ｍｍ２以下、７００００個／ｍｍ２以下、５００００個／ｍｍ２以下又は３００００個／ｍｍ２以下であってよい。 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.
＜回路接続用接着剤フィルムの製造方法＞
　上記回路接続用接着剤フィルム１０は、例えば、表面に複数のはんだ粒子２が配置された基体（例えば、表面に複数の凹部を有し、当該複数の凹部の少なくとも一部にはんだ粒子２が配置された基体）を用意すること（準備工程）と、該基体の該表面（例えば凹部が形成されている面）上に、第１の接着剤層３を設けることにより、第１の接着剤層３にはんだ粒子を転写すること（転写工程）と、第１の接着剤層３の一方面上に第２の接着剤層４を設けること（積層工程）と、を含む方法により製造することができる。この方法によれば、予めはんだ粒子が所定の配列で配置された基体を用いることにより、所定の配列を有し、単分散率にも優れる回路接続用接着剤フィルム１０を得ることができる。 <Manufacturing method of adhesive film for circuit connection>
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.
　以下、図４～図８を参照しながら、回路接続用接着剤フィルム１０の製造方法について説明する。図４は、回路接続用接着剤フィルム１０の製造方法に用いられる基体の縦断面を模式的に示す図であり、図５は、図４の基体の凹部の断面形状の変形例を示す図であり、図６は、図４の基体の凹部にはんだ粒子２が配置された状態を模式的に示す断面図であり、図７は、準備工程の一例を模式的に示す断面図であり、図８は、転写工程の一例を模式的に示す断面図である。なお、以下に説明する方法では、基体として、表面に複数の凹部を有し、当該複数の凹部の少なくとも一部にはんだ粒子２が配置された基体を用いるが、このような基体に限られず、例えば、はんだ粒子を固定可能な支持部（針等）を表面に備える基体などを用いることもできる。 Hereinafter, a method for manufacturing the circuit connection adhesive film 10 will be described with reference to FIGS. 4 to 8. 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, and 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, and 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. In the method described below, 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. For example, a substrate having a support portion (needle or the like) on which solder particles can be fixed can be used.
（準備工程）
　準備工程では、まず、表面に複数の凹部７を有する基体６を用意する（図４参照）。基体６は、複数の凹部７を有している。複数の凹部７は、例えば、所定のパターン（例えば、回路部材の電極パターンに対応するパターン）で規則的に配置されている。凹部７が所定のパターンで配置されている場合、はんだ粒子２が所定のパターンで第１の接着剤層に転写されることとなる。そのため、はんだ粒子２が所定のパターン（図２及び図３に示されるようなパターン）で規則的に配置された回路接続用接着剤フィルム１０が得られる。 (Preparation process)
In the preparation step, first, 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). When the recesses 7 are arranged in a predetermined pattern, the solder particles 2 are transferred to the first adhesive layer in a predetermined pattern. Therefore, a circuit connection adhesive film 10 in which the solder particles 2 are regularly arranged in a predetermined pattern (a pattern as shown in FIGS. 2 and 3) can be obtained.
　基体６の凹部７は、例えば、図４に示されるように、凹部７の底部７ａ側から基体６の表面６ａ側に向けて開口面積が拡大するテーパ状に形成されていてよい。すなわち、凹部７の底部７ａの幅（図４における幅ａ）は、凹部７の開口の幅（図４における幅ｂ）よりも狭くてよい。凹部７のサイズ（幅ａ、幅ｂ、容積、テーパ角度及び深さ等）は、目的とするはんだ粒子のサイズ、回路接続用接着剤フィルムにおけるはんだ粒子の位置に応じて設定することができる。例えば、凹部７の開口の幅（幅ｂ）は、はんだ粒子２の最大粒子径よりも大きくてよく、はんだ粒子の最大粒子径の２倍未満であってよい。 As shown in FIG. 4, 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 (width a, width b, volume, taper angle, depth, etc.) 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.
　基体６の縦断面における凹部７の形状（凹部７の断面形状）は、例えば、図５の（ａ）～（ｈ）に示されるような形状であってもよい。図５の（ａ）～（ｈ）に示されるいずれの断面形状も、凹部７の開口の幅（幅ｂ）が、断面形状における最大幅となっている。これにより、凹部７に配置されたはんだ粒子が取り出しやすくなり、作業性が向上する。 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. In any of the cross-sectional shapes 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. As a result, the solder particles arranged in the recess 7 can be easily taken out, and the workability is improved.
　凹部７の開口の形状は、円形、楕円形、三角形、四角形、多角形等であってよい。 The shape of the opening of the recess 7 may be a circle, an ellipse, a triangle, a quadrangle, a polygon, or the like.
　基体６の凹部７は、リソグラフィー、機械加工等の公知の方法によって形成することができる。これらの方法では、凹部のサイズ及び形状を自在に設計可能である。 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.
　基体６を構成する材料としては、例えば、シリコン、各種セラミックス、ガラス、ステンレススチール等の金属等の無機材料、並びに、各種樹脂等の有機材料を使用することができる。後述するように、本実施形態の製造方法では、はんだ粒子２を基体６の凹部７内で形成することにより基体６の凹部７にはんだ粒子２を配置することができるが、この場合、基体６は、はんだ粒子２の形成に使用する微粒子の溶融温度で変質しない耐熱性を有していてよい。 As the material constituting the substrate 6, for example, an inorganic material such as silicon, various ceramics, glass, a metal such as stainless steel, and an organic material such as various resins can be used. As will be described later, in the manufacturing method of the present embodiment, 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.
　次に、基体６の複数の凹部７の少なくとも一部（一部又は全部）にはんだ粒子２を配置（収容）する（図６参照）。 Next, the 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).
　はんだ粒子２の配置方法は特に限定されない。配置方法は、乾式、湿式のいずれであってもよい。例えば、はんだ粒子２を基体６の表面６ａ上に配置し、スキージ又は微粘着ローラーを用いて、基体６の表面６ａを擦ることで、余分なはんだ粒子２を除去しつつ、凹部７にはんだ粒子２を配置することができる。凹部７の開口の幅ｂが凹部７の深さより大きい場合、凹部７の開口からはんだ粒子が飛び出す場合がある。スキージを用いると、凹部７の開口から飛び出ているはんだ粒子は除去される。余分なはんだ粒子を除去する方法として、圧縮空気を吹き付ける、不織布又は繊維の束で基体６の表面６ａを擦る方法も挙げられる。これらの方法は、スキージと比べて物理的な力が弱いため、はんだ粒子として、変形しやすい粒子（例えばはんだ粒子）を扱う上で好ましい。 The method of arranging the solder particles 2 is not particularly limited. The arrangement method may be either dry type or wet type. For example, 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. When 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. When a squeegee is used, the solder particles protruding from the opening of the recess 7 are removed. 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.
　回路接続用接着剤フィルム１０の製造方法では、基体６の凹部７内ではんだ粒子２を形成することにより、はんだ粒子２を凹部７に配置してもよい。具体的には、例えば、図７に示されるように、はんだ粒子２を形成するための微粒子８を凹部７内に収容した後、凹部７に収容された微粒子８を融合させることで、凹部７内ではんだ粒子２を形成することができる。凹部７内に収容された微粒子８は、溶融することで合一化し、表面張力によって球状化するが、このとき、凹部７の底部７ａとの接触部では、溶融した金属が底部７ａに追従した形状となる。そのため、例えば、凹部７の底部７ａが図７に示されるような平坦な形状である場合、はんだ粒子２は、表面の一部に平面部２ａを有するものとなる。 In the method for manufacturing the adhesive film 10 for circuit connection, 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.
　微粒子８は、凹部７内に収容することができればよく、粒度分布にばらつきが大きくても、形状がいびつであってもよい。 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.
　凹部７に収容された微粒子８を溶融させる方法としては、微粒子８を当該微粒子を形成する材料（はんだ）の融点以上に加熱する方法が挙げられる。微粒子８は、酸化被膜の影響で融点以上の温度で加熱しても溶融しない、濡れ拡がらない、又は合一化しない場合がある。このため、微粒子８を還元雰囲気下に晒し、微粒子８の表面酸化皮膜を除去した後に、微粒子８の融点以上の温度に加熱することで、微粒子８を溶融させ、濡れ拡がり、合一化させることができる。同様の観点から、微粒子８の溶融は、還元雰囲気下で行ってよい。 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.
　還元雰囲気にする方法は、上述の効果が得られる方法であれば特に限定されず、例えば水素ガス、水素ラジカル、ギ酸ガス等を用いる方法がある。例えば、水素還元炉、水素ラジカル還元炉、ギ酸還元炉、又はこれらのコンベアー炉若しくは連続炉を用いることで、還元雰囲気下で微粒子８を溶融させることができる。これらの装置は、炉内に、加熱装置、不活性ガス（窒素、アルゴン等）を充填するチャンバー、チャンバー内を真空にする機構等を備えていてよく、これにより還元ガスの制御がより容易となる。また、チャンバー内を真空にできると、微粒子８の溶融及び合一化の後に、減圧によってボイドの除去を行うことができ、接続安定性に一層優れるはんだ粒子２を得ることができる。 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. For example, by using 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.
　微粒子８の還元、溶解条件、温度、炉内雰囲気調整などのプロファイルは、微粒子８の融点、粒度、凹部のサイズ、基体６の材質などを勘案して適宜設定されてよい。 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.
　上記方法によれば、微粒子８の材質及び形状によらず、略均一なサイズのはんだ粒子２を形成することができる。また、はんだ粒子２のサイズ及び形状は凹部７に収容される微粒子８の量、凹部７の形状等に依存するため、凹部７の設計（凹部のサイズ、形状等の調整）によりはんだ粒子２のサイズ及び形状を自在に設計でき、目的の粒度分布を有するはんだ粒子（平均粒子径が１～３０μｍであり、且つ、粒子径のＣ．Ｖ．値が２０％以下であるはんだ粒子）を容易に準備することができる。 According to the above method, 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 μm and a CV value of the particle size of 20% or less) can be easily produced. I can prepare.
　上記方法は、特に、はんだ粒子２が、インジウム系はんだ粒子である場合に好適である。すなわち、インジウム系はんだは、めっきによる析出が可能であるが、粒子状に析出させることは難しく、柔らかくて扱いが難しい材料である。しかし、上記方法では、インジウム系はんだ微粒子を原料として用いることで、略均一な粒子径を有するインジウム系はんだ粒子を容易に製造することができる。 The above method is particularly suitable when the 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. However, in the above method, by using indium-based solder fine particles as a raw material, indium-based solder particles having a substantially uniform particle size can be easily produced.
　はんだ粒子２を凹部７に配置した後は、はんだ粒子２が凹部７に配置（収容）された状態で基体６を取り扱うことができる。例えば、基体６をはんだ粒子２が凹部７に配置（収容）された状態で運搬・保管等する場合、はんだ粒子２の変形を防止することができる。また、はんだ粒子２が凹部７に配置（収容）された状態では、はんだ粒子２の取り出しが容易であるため、はんだ粒子２を回収・表面処理等を行う際の変形も防止しやすい。 After the solder particles 2 are arranged in the recesses 7, 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.
（転写工程）
　転写工程では、基体６の表面（凹部７が形成されている面）上に、第１の接着剤層３を設けることにより、第１の接着剤層３にはんだ粒子２を転写する（図８参照）。 (Transfer process)
In the transfer step, the 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).
　具体的には、まず、支持体１１上に、第１の接着剤層３を形成して積層フィルム１２を得た後、基体６の凹部７が形成されている面（基体６の表面）６ａと、積層フィルム１２の第１の接着剤層３側の面（第１の接着剤層３の支持体１１とは反対側の面）とを対向させて、基体６と第１の接着剤層３とを近づける（図８の（ａ）参照）。次に、積層フィルム１２と基体６とを貼り合わせることで第１の接着剤層３を基体６の表面（凹部７が形成されている面）６ａに接触させて、第１の接着剤層３にはんだ粒子２を転写する。これにより、第１の接着剤層３と、少なくとも一部が第１の接着剤層３中に埋め込まれたはんだ粒子２と、を備える粒子転写層１３が得られる（図８の（ｂ）参照）。この際、図８の（ｂ）に示されるように、凹部７の底部が平坦である場合、はんだ粒子２が凹部７の底部の形状に対応して平面部２ａを有することとなり、当該平面部２ａが支持体１１とは反対側を向いた状態で、第１の接着剤層３中に配置される。 Specifically, first, 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). Next, 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. As a result, 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). ). At this time, as shown in FIG. 8B, 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.
　第１の接着剤層３は、第１の接着剤層３の構成成分を、有機溶媒中で撹拌混合、混練等を行うことによって溶解又は分散させて調製される、ワニス組成物（ワニス状の第１の接着剤組成物）を用いて形成することができる。具体的には、例えば、支持体１１（例えば離型処理を施した基材）上に、ワニス組成物をナイフコーター、ロールコーター、アプリケーター、コンマコーター、ダイコーター等を用いて塗布した後、加熱によって有機溶媒を揮発させることで、第１の接着剤層３を形成することができる。このとき、ワニス組成物の塗布量を調整することによって、最終的に得られる第１の接着剤層の厚さを調整することができる。 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.
　ワニス組成物の調製において使用される有機溶媒は、各成分を略均一に溶解又は分散し得る特性を有するものであれば特に制限されない。このような有機溶媒としては、例えば、トルエン、アセトン、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸プロピル、酢酸ブチル等が挙げられる。これらの有機溶媒は、単独で又は２種以上を組み合わせて使用することができる。ワニス組成物の調製の際の撹拌混合又は混練は、例えば、撹拌機、らいかい機、３本ロール、ボールミル、ビーズミル、ホモディスパー等を用いて行うことができる。 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.
　支持体１１は、有機溶媒を揮発させる際の加熱条件に耐え得る耐熱性を有するものであれば特に制限されない。支持体１１はプラスチックフィルムであってもよいし、金属箔であってもよい。支持体１１としては、例えば、延伸ポリプロピレン（ＯＰＰ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリオレフィン、ポリアセテート、ポリカーボネート、ポリフェニレンサルファイド、ポリアミド、ポリイミド、セルロース、エチレン・酢酸ビニル共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、合成ゴム系、液晶ポリマー等を構成材料とする基材（例えば、フィルム）などを用いてよい。 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.
　基材へ塗布したワニス組成物から有機溶媒を揮発させる際の加熱条件は、使用する有機溶媒等に合わせて適宜設定することができる。加熱条件は、例えば、４０～１２０℃で０．１～１０分間であってよい。 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.
　第１の接着剤層３には、溶剤の一部が除去されずに残っていてもよい。第１の接着剤層３における溶剤の含有量は、例えば、第１の接着剤層３の全質量を基準として、１０質量％以下であってよい。 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.
　積層フィルム１２と基体６とを貼り合わせる方法としては、例えば、加熱プレス、ロールラミネート、真空ラミネート等の方法が挙げられる。ラミネートは、例えば、０～８０℃の温度条件下で行うことができる。 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.
　転写工程では、ワニス組成物を基体６に直接塗布することで第１の接着剤層３を形成してもよいが、上記の方法のように積層フィルム１２を用いることで、支持体１１と第１の接着剤層３とはんだ粒子２が一体となった粒子転写層１３が得られやすくなる。 In the transfer step, 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.
（積層工程）
　積層工程では、第１の接着剤層３の支持体１１とは反対側（はんだ粒子２が転写された側）の面上に第２の接着剤層４を設ける。これにより、図１に示される回路接続用接着剤フィルム１０が得られる。 (Laminating process)
In the laminating step, 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.
　第２の接着剤層４は、ワニス状の第１の接着剤組成物に代えて、第２の接着剤層４の構成成分を、有機溶媒中で撹拌混合、混練等を行うことによって溶解又は分散させて調製される、ワニス組成物（ワニス状の第２の接着剤組成物）を用いること以外は、第１の接着剤層３を基体６上に設ける方法と同様にして、第１の接着剤層３上に設けることができる。すなわち、第２の接着剤層４を支持体上に形成して得られる積層フィルムと第１の接着剤層３とを貼り合わせることで第１の接着剤層３上に第２の接着剤層４を設けてよく、ワニス状の第２の接着剤組成物を第１の接着剤層３に直接塗布することで第１の接着剤層３上に第２の接着剤層４を設けてもよい。 In the second adhesive layer 4, instead of the varnish-like first adhesive composition, 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.
　積層工程では、支持体１１を剥離した後に当該支持体１１が設けられていた側の面上に第２の接着剤層４を設けてもよいが、上記の方法のように支持体１１とは反対側の面上に第２の接着剤層４を設けることで、回路部材への回路接続用接着剤フィルムの貼り付け性向上及び接続時の剥離抑制が期待できる。 In the laminating step, 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.
　以上、回路接続用接着剤フィルム１０及びその製造方法を例に挙げて本発明の回路接続用接着剤フィルムの製造方法について説明したが、本発明は上記実施形態に限定されない。 Although the method for manufacturing the circuit connection adhesive film of the present invention has been described above by taking the circuit connection adhesive film 10 and the method for manufacturing the same as an example, the present invention is not limited to the above embodiment.
　例えば、回路接続用接着剤フィルム１０における接着剤フィルム１が、第１の接着剤層３のみからなっていてもよく、第１の接着剤層３及び第２の接着剤層４以外の他の接着剤層を更に備えていてもよい。 For example, 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.
＜接続構造体及びその製造方法＞
　以下、接続材料として上述の回路接続用接着剤フィルム１０を用いた接続構造体（回路接続構造体）及びその製造方法について説明する。 <Connection structure and its manufacturing method>
Hereinafter, a 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.
　図９は、接続構造体の一実施形態を示す模式断面図である。図９に示すように、接続構造体１００は、第１の回路基板２１及び第１の回路基板２１の主面２１ａ上に形成された第１の電極２２を有する第１の回路部材２３と、第２の回路基板２４及び第２の回路基板２４の主面２４ａ上に形成された第２の電極２５を有する第２の回路部材２６と、第１の電極２２と第２の電極２５とをはんだ層３０を介して互いに電気的に接続し且つ第１の回路部材２３と第２の回路部材２６とを接着する接続部２７と、を備えている。 FIG. 9 is a schematic cross-sectional view showing an embodiment of the connection structure. As shown in FIG. 9, 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.
　第１の回路部材２３及び第２の回路部材２６は、互いに同じであっても異なっていてもよい。第１の回路部材２３及び第２の回路部材２６は、回路電極が形成されているガラス基板又はプラスチック基板；プリント配線板；セラミック配線板；フレキシブル配線板；駆動用ＩＣ等のＩＣチップなどであってよい。第１の回路基板２１及び第２の回路基板２４は、半導体、ガラス、セラミック等の無機物、ポリイミド、ポリカーボネート等の有機物、ガラス／エポキシ等の複合物などで形成されていてよい。第１の回路基板２１は、プラスチック基板であってよい。第１の回路部材２３は、例えば、回路電極が形成されているプラスチック基板（ポリイミド、ポリカーボネート、ポリエチレンテレフタレート、シクロオレフィンポリマー等の有機物を構成材料とするプラスチック基板）であってよく、第２の回路部材２６は、例えば、駆動用ＩＣ等のＩＣチップであってよい。電極が形成されているプラスチック基板は、プラスチック基板上に、例えば、有機ＴＦＴ等の画素駆動回路又は複数の有機ＥＬ素子Ｒ、Ｇ、Ｂがマトリクス状に規則配列されることによって表示領域が形成されたものであってもよい。 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. In the plastic substrate on which the electrodes are formed, 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.
　第１の電極２２及び第２の電極２５は、金、銀、錫、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金、銅、アルミ、モリブデン、チタン等の金属、インジウム錫酸化物（ＩＴＯ）、インジウム亜鉛酸化物（ＩＺＯ）、インジウムガリウム亜鉛酸化物（ＩＧＺＯ）等の酸化物などを含む電極であってよい。第１の電極２２及び第２の電極２５は、これら金属、酸化物等の２種以上を積層してなる電極であってもよい。２種以上を積層してなる電極は、２層以上であってよく、３層以上であってよい。第１の電極２２及び第２の電極２５は回路電極であってよく、バンプ電極であってもよい。図９では、第１の電極２２が回路電極であり、第２の電極２５がバンプ電極である。 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.
　第１の電極２２の高さと第２の電極２５の高さの合計値は、接続部２７を形成するために用いられる回路接続用接着剤フィルム中のはんだ粒子２の平均粒子径よりも小さくてよい。合計値は、例えば、３０μｍ以下、２０μｍ以下、１５μｍ以下、１０μｍ以下、５μｍ以下、４μｍ未満、３μｍ未満、２μｍ未満又は１μｍ未満であってよい。第１の電極２２の高さ（例えば回路電極の高さ）は、例えば、０．０５～５．０μｍ、０．１～４．０μｍ又は０．５～３．０μｍであってよい。第２の電極２５の高さ（例えばバンプ電極の高さ）は、例えば、０．５～２５．０μｍ、２．０～１５．０μｍ又は５．０～１０．０μｍであってよい。 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 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 5 μm or less, less than 4 μm, less than 3 μm, less than 2 μm, or less than 1 μm. The height of the first electrode 22 (for example, the height of the circuit electrode) may be, for example, 0.05 to 5.0 μm, 0.1 to 4.0 μm, or 0.5 to 3.0 μm. The height of the second electrode 25 (for example, the height of the bump electrode) may be, for example, 0.5 to 25.0 μm, 2.0 to 15.0 μm, or 5.0 to 10.0 μm.
　接続部２７は、回路接続用接着剤フィルム１０の硬化物である。接続部２７は、例えば、第１の回路部材２３と第２の回路部材２６とが互いに対向する方向（以下「対向方向」）における第１の回路部材２３側に位置し、第１の接着剤層３の硬化物を含む第１の領域２８と、対向方向における第２の回路部材２６側に位置し、第２の接着剤層４の硬化物を含む第２の領域２９と、第１の電極２２及び第２の電極２５の間に介在して第１の電極２２と第２の電極２５とを互いに電気的に接続するはんだ層３０と、隣り合う電極間に位置するはんだ粒子２とを有している。はんだ粒子２は、接続部２７中で溶融した状態であってもよい。接続部２７は、第１の領域２８と第２の領域２９との間に、２つの明確な領域を有していなくてもよく、例えば、第１の接着剤層３と第２の接着剤層４とが混在した状態で硬化した領域を含んでいてもよい。 The 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 first region 28 containing a cured product of the layer 3 and a second region 29 located on the side of the second circuit member 26 in the opposite direction and containing the cured product of the second adhesive layer 4 and a first. 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.
　接続構造体としては、例えば、微細なＬＥＤ素子（発光素子）が規則的に配置されたプラスチック基板と、映像表示用のドライバーである駆動回路素子とが接続されたカラーディスプレイ、微細なＬＥＤ素子が規則的に配置されたプラスチック基板と、タッチパッド等の位置入力素子とが接続されたタッチパネルなどのマイクロＬＥＤ表示装置が挙げられる。接続構造体は、ＬＥＤ素子が有機ＥＬ素子である有機ＥＬ表示装置であってもよい。接続構造体は、スマートホン、タブレット、テレビ、乗り物のナビゲーションシステム、ウェアラブル端末等の各種モニタ；家具；家電；日用品などに適用することもできる。 Examples of the connection structure 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.
　図１０は、接続構造体１００の製造方法の一実施形態を示す模式断面図である。図１０の（ａ）及び図１０の（ｂ）は、各工程を示す模式断面図である。図１０に示すように、接続構造体１００の製造方法は、第１の回路部材２３の第１の電極２２が設けられている面と、第２の回路部材２６の第２の電極２５が設けられている面との間に、上述の回路接続用接着剤フィルム１０を配置することと、第１の回路部材２３と回路接続用接着剤フィルム１０と第２の回路部材２６とを含む積層体を当該積層体の厚さ方向に押圧した状態で加熱することにより、第１の電極２２と第２の電極２５とをはんだ層３０を介して互いに電気的に接続し且つ第１の回路部材２３と第２の回路部材２６とを接着することとを含む。 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. As shown in FIG. 10, in the method of manufacturing the connection structure 100, 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. 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.
　具体的には、まず、第１の回路基板２１及び第１の回路基板２１の主面２１ａ上に形成された第１の電極２２を備える第１の回路部材２３と、第２の回路基板２４及び第２の回路基板２４の主面２４ａ上に形成された第２の電極２５を備える第２の回路部材２６とを準備する。 Specifically, first, 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. And a second circuit member 26 having a second electrode 25 formed on the main surface 24a of the second circuit board 24 are prepared.
　次に、第１の回路部材２３及び第２の回路部材２６を、第１の電極２２及び第２の電極２５が互いに対向するように配置し、第１の回路部材２３と第２の回路部材２６との間に回路接続用接着剤フィルム１０を配置する。例えば、図１０の（ａ）に示すように、第１の接着剤層３側が第１の回路基板２１の主面２１ａと対向するようにして回路接続用接着剤フィルム１０を第１の回路部材２３上にラミネートする。次に、第１の回路基板２１上の第１の電極２２と、第２の回路基板２４上の第２の電極２５とが互いに対向するように、回路接続用接着剤フィルム１０がラミネートされた第１の回路部材２３上に第２の回路部材２６を配置する。 Next, 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. For example, as shown in FIG. 10A, 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. Next, 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.
　そして、図１０の（ｂ）に示すように、第１の回路部材２３と、回路接続用接着剤フィルム１０と、第２の回路部材２６とがこの順で積層されてなる積層体を当該積層体の厚さ方向に押圧した状態で加熱することで、第１の回路部材２３と第２の回路部材２６とを互いに熱圧着する。この際、図１０の（ｂ）において矢印で示すように、第１の接着剤層３及び第２の接着剤層４中に含まれる流動可能な未硬化の熱硬化性成分が、互いに隣り合う電極の空隙（第１の電極２２同士の間の空隙、及び、第２の電極２５同士の間の空隙）を埋めるように流動すると共に、上記加熱によって硬化する。また、押圧した状態で加熱されることによりはんだ粒子２が溶融し、第１の電極２２と第２の電極２５との間に寄り集まって、はんだ層３０が形成され、その後、冷却することで第１の電極２２と第２の電極２５の間にはんだ層３０が固着される。これにより、第１の電極２２及び第２の電極２５がはんだ層３０（はんだ粒子２の溶融固化物）を介して互いに電気的に接続され、また、第１の回路部材２３及び第２の回路部材２６が互いに接着されて、図９に示す接続構造体１００が得られる。 Then, as shown in 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. By heating while pressing in the thickness direction of the body, the first circuit member 23 and the second circuit member 26 are thermocompression-bonded to each other. At this time, as shown by an arrow in FIG. 10B, 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. Further, the 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. As a result, 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.
　接続時の加熱温度は、はんだ粒子が溶融可能な温度（例えば、はんだ粒子の融点よりも高い温度）であればよく、例えば、１３０～２６０℃であってよい。加圧は、被着体に損傷を与えない範囲であれば特に制限されないが、例えば、チップの面積換算圧力０．１～５０ＭＰａであってよく、４０ＭＰａ以下であってよく、０．１～４０ＭＰａであってよい。これらの加熱及び加圧の時間は、０．５～３００秒間の範囲であってよい。 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.
　以下、本発明の内容を実施例及び比較例を用いてより詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the contents of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
＜材料の用意＞
　実施例及び比較例では、接着剤フィルムの材料として、以下に示す材料を用いた。 <Preparation of materials>
In the examples and comparative examples, the following materials were used as the material of the adhesive film.
（Ａ：カチオン重合性化合物）
Ａ１：セロキサイド８０１０（ビ－７－オキサビシクロ［４．１．０］ヘプタン、株式会社ダイセル製）
Ａ２：ＥＴＥＲＮＡＣＯＬＬ　ＯＸＢＰ（４，４’－ビス［３－エチル－３－オキセタニル］メトキシメチル］ビフェニル、宇部興産株式会社製）
Ａ３：ｊＥＲ１０１０（ビスフェノールＡ型固形エポキシ樹脂、三菱化学株式会社製） (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：熱カチオン重合開始剤（熱潜在性カチオン発生剤））
Ｂ１：ＣＸＣ－１８２１（第４級アンモニウム塩型熱酸発生剤、Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製） (B: Thermal cation polymerization initiator (thermal latent cation generator))
B1: CXC-1821 (Quaternary ammonium salt type thermoacid generator, manufactured by King Industries)
（Ｃ：熱可塑性樹脂）
Ｃ１：Ｐ－１（後述の方法で合成したフルオレン型フェノキシ樹脂）
Ｃ２：ＹＰ－７０（ビスフェノールＡ・ビスフェノールＦ共重合型フェノキシ樹脂、日鉄ケミカル＆マテリアル株式会社製） (C: Thermoplastic resin)
C1: 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.)
［Ｐ－１の合成］
　４，４’－（９－フルオレニリデン）－ジフェノール４５ｇ（シグマアルドリッチジャパン株式会社製）、及び３，３’，５，５’－テトラメチルビフェノールジグリシジルエーテル５０ｇ（ＹＸ－４０００Ｈ、三菱化学株式会社製）を、ジムロート冷却管、塩化カルシウム管、及び攪拌モーターに接続されたＰＴＦＥ製攪拌棒を装着した３０００ｍＬの３つ口フラスコ中でＮ－メチルピロリドン１０００ｍＬに溶解して反応液とした。これに炭酸カリウム２１ｇを加え、マントルヒーターで１１０℃に加熱しながら攪拌した。３時間攪拌後、１０００ｍＬのメタノールが入ったビーカーに反応液を滴下し、生成した沈殿物を吸引ろ過することによってろ取した。ろ取した沈殿物をさらに３００ｍＬのメタノールで３回洗浄して、フェノキシ樹脂Ｐ－１を７５ｇ得た。 [Synthesis of P-1]
4,4'-(9-fluorenylidene) -diphenol 45 g (manufactured by Sigma Aldrich Japan Co., Ltd.) and 3,3', 5,5'-tetramethylbiphenol diglycidyl ether 50 g (YX-4000H, Mitsubishi Chemical Co., Ltd.) Was dissolved in 1000 mL of N-methylpyrrolidone in a 3000 mL three-necked flask equipped with a Dimroth condenser, a calcium chloride tube, and a PTFE stirring rod connected to a stirring motor to prepare a reaction solution. 21 g of potassium carbonate was added thereto, and the mixture was stirred while heating to 110 ° C. with a mantle heater. After stirring for 3 hours, the reaction solution was added dropwise to a beaker containing 1000 mL of methanol, and the generated precipitate was collected by suction filtration. The precipitate collected by filtration was further washed 3 times with 300 mL of methanol to obtain 75 g of phenoxy resin P-1.
　その後、フェノキシ樹脂Ｐ－１の分子量を東ソー株式会社製高速液体クロマトグラフＧＰ８０２０を用いて測定した（カラム：日立化成株式会社製Ｇｅｌｐａｋ　ＧＬ－Ａ１５０Ｓ及びＧＬＡ１６０Ｓ、溶離液：テトラヒドロフラン、流速：１．０ｍｌ／分）。その結果、ポリスチレン換算でＭｎ＝１５７６９、Ｍｗ＝３８０４５、Ｍｗ／Ｍｎ＝２．４１３であった。 Then, the molecular weight of the phenoxy resin P-1 was measured using a high performance liquid chromatograph GP8020 manufactured by Tosoh Corporation (column: Gelpac GL-A150S and GLA160S manufactured by Hitachi Chemical Co., Ltd., eluent: tetrahydrofuran, flow velocity: 1.0 ml / Minutes). As a result, it was Mn = 15769, Mw = 38045, and Mw / Mn = 2.413 in terms of polystyrene.
（Ｄ：充填剤）
Ｄ１：アエロジルＲ８０５（トリメトキシオクチルシランとシリカの加水分解生成物（シリカ微粒子）、Ｅｖｏｎｉｋ　Ｉｎｄｕｓｔｒｉｅｓ　ＡＧ社製、有機溶媒で不揮発分１０質量％に希釈したものを使用）
Ｄ２：表面処理されたシリカ粒子（シリカとビス（トリメチルシリル）アミンとの加水分解生成物） (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：カップリング剤）
Ｅ１：ＫＢＭ－４０３（γ―グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社製） (E: Coupling agent)
E1: KBM-403 (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
＜基体の準備＞
　表面に複数の凹部を有する基体（Ａ）（ＰＥＴフィルム、厚さ：５５μｍ）、基体（Ｂ）（ＰＥＴフィルム、厚さ：５４μｍ）及び基体（Ｃ）（ＰＥＴフィルム、厚さ：５７μｍ）を用意した。 <Preparation of substrate>
Prepare a substrate (A) (PET film, thickness: 55 μm), a substrate (B) (PET film, thickness: 54 μm) and a substrate (C) (PET film, thickness: 57 μm) having a plurality of recesses on the surface. did.
　基体（Ａ）の凹部は、基体の表面側に向けて開口面積が拡大する円錐台状（開口部上面からみると、底部の中心と開口部の中心は同一）とし、開口径は４．３μｍφ、底部径は４．０μｍφ、深さは４．０μｍとした。また、基体（Ａ）の複数の凹部は、６．２μｍの間隔（各底部の中心間距離）で三方配列にて規則的に１ｍｍ四方辺り２９，０００個となるように形成した。 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 μmφ. The bottom diameter was 4.0 μmφ and the depth was 4.0 μm. Further, the plurality of recesses of the substrate (A) were regularly formed in a three-way arrangement at an interval of 6.2 μm (distance between the centers of the bottoms) so as to be 29,000 per 1 mm square.
　基体（Ｂ）の凹部は、基体の表面側に向けて開口面積が拡大する円錐台状（開口部上面からみると、底部の中心と開口部の中心は同一）とし、開口径は３．３μｍφ、底部径は３．０μｍφ、深さは３．０μｍとした。また、複数の凹部は、６．２μｍの間隔（各底部の中心間距離）で三方配列にて規則的に１ｍｍ四方辺り２９，０００個となるように形成した。 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 μmφ. The bottom diameter was 3.0 μmφ and the depth was 3.0 μm. Further, the plurality of recesses were regularly formed in a three-way arrangement at an interval of 6.2 μm (distance between the centers of the bottoms) so as to be 29,000 per 1 mm square.
　基体（Ｃ）の凹部は、基体の表面側に向けて開口面積が拡大する円錐台状（開口部上面からみると、底部の中心と開口部の中心は同一）とし、開口径は５．３μｍφ、底部径は５．０μｍφ、深さは５．０μｍとした。また、複数の凹部は、６．２μｍの間隔（各底部の中心間距離）で三方配列にて規則的に１ｍｍ四方辺り２９，０００個となるように形成した。 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 μmφ. The bottom diameter was 5.0 μmφ and the depth was 5.0 μm. Further, the plurality of recesses were regularly formed in a three-way arrangement at an interval of 6.2 μm (distance between the centers of the bottoms) so as to be 29,000 per 1 mm square.
＜実施例１～８、比較例１～６＞
　以下に示す方法で、表１に示す組成を有する接着剤フィルムと、当該接着剤フィルム中に配置された導電粒子と、を備える実施例１～８及び比較例１～６の異方導電性接着剤フィルムを作製した。なお、工程（ａ）として、実施例１～５、比較例１～３及び比較例５では工程（ａ１）を実施し、実施例６では工程（ａ２）を実施し、実施例７及び比較例４では工程（ａ３）を実施し、実施例８では工程（ａ４）を実施し、比較例６では工程（ａ５）を実施した。 <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. As 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. In 4, 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.
（工程（ａ）：準備工程）
［工程（ａ１）：はんだ粒子（種類：Ｆ１、平均粒子径：４．０μｍ）の作製及び配置］
　Ｓｎ－Ｂｉはんだ微粒子（５Ｎ　Ｐｌｕｓ社製、融点１３８℃、Ｔｙｐｅ８）１００ｇを、蒸留水に浸漬し、超音波分散させた後、整地し、上澄みに浮遊するはんだ微粒子を回収した。この操作を繰り返して、１０ｇのはんだ微粒子を回収した。得られたはんだ微粒子の平均粒子径は１．０μｍ、粒子径のＣ．Ｖ．値は４２％であった。次いで、得られたはんだ微粒子（平均粒子径：１．０μｍ、粒子径のＣ．Ｖ．値：４２％）を基体（Ａ）の、凹部が形成されている面上に配置した。次いで、基体（Ａ）の凹部が形成されている面を微粘着ローラーで擦ることで余分なはんだ微粒子を取り除き、凹部内のみにはんだ微粒子を配置した。次いで、凹部にはんだ微粒子が配置された基体を、水素ラジカル還元炉（神港精機株式会社製、水素プラズマリフロー装置）に投入し、真空引き後、水素ガスを炉内に導入して、炉内を水素ガスで満たした。その後、炉内を１２０℃に調整し、５分間水素ラジカルを照射した。その後、真空引きにて炉内の水素ガスを除去し、１４５℃まで加熱した後、窒素を炉内に導入して大気圧に戻してから炉内の温度を室温まで下げることによりはんだ粒子を形成した。これにより、工程（ｂ２）で使用する、凹部に導電粒子（はんだ粒子）が配置された基体を用意した。 (Step (a): Preparation step)
[Step (a1): Preparation and arrangement of solder particles (type: F1, average particle diameter: 4.0 μm)]
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 μm, and the particle size was C.I. V. The value was 42%. Next, the obtained solder fine particles (average particle diameter: 1.0 μm, CV value of particle diameter: 42%) were placed on the surface of the substrate (A) where the recesses were formed. Next, 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. Next, 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. Then, the temperature inside the furnace was adjusted to 120 ° C., and hydrogen radicals were irradiated for 5 minutes. After that, 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. As a result, a substrate in which conductive particles (solder particles) were arranged in the concave portions, which was used in the step (b2), was prepared.
　別途同様の操作ではんだ粒子を作製し、得られたはんだ粒子を、基体の凹部の裏側をタップすることで凹部より回収した。はんだ粒子は表面の一部に平面部を有し、はんだ粒子の直径Ａに対する平面部の直径Ｂの比（Ｂ／Ａ）が０．３５であることを確認した。また、はんだ粒子の投影像に外接する四角形を二対の平行線により作成したところ、対向する辺間の距離をＸ及びＹ（但しＹ＜Ｘ）としたときに、Ｙ／Ｘが０．９３であることを確認した。また、はんだ粒子の平均粒子径及び粒子径のＣ．Ｖ．値を測定したところ、平均粒子径は４．０μｍであり、粒子径のＣ．Ｖ．値は７．９％であった。なお、はんだ粒子の平均粒子径、Ｂ／Ａ、Ｙ／Ｘは、工程（ｂ）において作製した粒子転写層を、１０ｃｍ×１０ｃｍに切り出し、はんだ粒子が配置されている面にＰｔスパッタを施した後、３００個のはんだ粒子をＳＥＭ観察して測定された値である。 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. When the value was measured, the average particle size was 4.0 μm, and the particle size C.I. V. The value was 7.9%. For the average particle diameters of the solder particles, B / A and Y / X, 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.
［工程（ａ２）：はんだ粒子（種類：Ｆ１、平均粒子径：３．０μｍ）の作製及び配置］
　基体（Ａ）に代えて基体（Ｂ）を用いたことを除き、工程（ａ１）と同様にして、はんだ粒子を形成し、工程（ｂ２）で使用する、凹部に導電粒子（はんだ粒子）が配置された基体を用意した。 [Step (a2): Preparation and arrangement of solder particles (type: F1, average particle diameter: 3.0 μm)]
Solder particles are formed in the same manner as in step (a1) except that the substrate (B) is used instead of the substrate (A), and conductive particles (solder particles) are formed in the recesses used in the step (b2). The arranged substrate was prepared.
　別途同様の操作ではんだ粒子を作製し、得られたはんだ粒子を、基体の凹部の裏側をタップすることで凹部より回収した。はんだ粒子は表面の一部に平面部を有し、はんだ粒子の直径Ａに対する平面部の直径Ｂの比（Ｂ／Ａ）が０．４０であることを確認した。また、はんだ粒子の投影像に外接する四角形を二対の平行線により作成したところ、対向する辺間の距離をＸ及びＹ（但しＹ＜Ｘ）としたときに、Ｙ／Ｘが０．９３であることを確認した。また、はんだ粒子の平均粒子径及び粒子径のＣ．Ｖ．値を測定したところ、平均粒子径は３．０μｍであり、粒子径のＣ．Ｖ．値は８．８％であった。なお、はんだ粒子の平均粒子径、Ｂ／Ａ、Ｙ／Ｘは、工程（ｂ）において作製した粒子転写層を、１０ｃｍ×１０ｃｍに切り出し、はんだ粒子が配置されている面にＰｔスパッタを施した後、３００個のはんだ粒子をＳＥＭ観察して測定された値である。 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. When the value was measured, the average particle size was 3.0 μm, and the particle size C.I. V. The value was 8.8%. For the average particle diameters of the solder particles, B / A and Y / X, 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.
［工程（ａ３）：はんだ粒子（種類：Ｆ１、平均粒子径：５．０μｍ）の作製及び配置］
　基体（Ａ）に代えて基体（Ｃ）を用いたことを除き、工程（ａ１）と同様にして、はんだ粒子を形成し、工程（ｂ２）で使用する、凹部に導電粒子（はんだ粒子）が配置された基体を用意した。 [Step (a3): Preparation and arrangement of solder particles (type: F1, average particle diameter: 5.0 μm)]
Solder particles are formed in the same manner as in step (a1) except that the substrate (C) is used instead of the substrate (A), and conductive particles (solder particles) are formed in the recesses used in the step (b2). The arranged substrate was prepared.
　別途同様の操作ではんだ粒子を作製し、得られたはんだ粒子を、基体の凹部の裏側をタップすることで凹部より回収した。はんだ粒子は表面の一部に平面部を有し、はんだ粒子の直径Ａに対する平面部の直径Ｂの比（Ｂ／Ａ）が０．４４であることを確認した。また、はんだ粒子の投影像に外接する四角形を二対の平行線により作成したところ、対向する辺間の距離をＸ及びＹ（但しＹ＜Ｘ）としたときに、Ｙ／Ｘが０．９３であることを確認した。また、はんだ粒子の平均粒子径及び粒子径のＣ．Ｖ．値を測定したところ、平均粒子径は５．０μｍであり、粒子径のＣ．Ｖ．値は７．６％であった。なお、はんだ粒子の平均粒子径、Ｂ／Ａ、Ｙ／Ｘは、工程（ｂ）において作製した粒子転写層を、１０ｃｍ×１０ｃｍに切り出し、はんだ粒子が配置されている面にＰｔスパッタを施した後、３００個のはんだ粒子をＳＥＭ観察して測定された値である。 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. When the value was measured, the average particle size was 5.0 μm, and the particle size C.I. V. The value was 7.6%. For the average particle diameters of the solder particles, B / A and Y / X, 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.
［工程（ａ４）：はんだ粒子（種類：Ｆ２、平均粒子径：４．０μｍ）の作製及び配置］
　Ｓｎ－Ｂｉはんだ微粒子に代えてＳｎ－Ａｇ－Ｃｕはんだ微粒子（三井金属工業株式会社製、融点２１９℃、ＳＴ－３）を用いたこと、水素ラジカル還元炉の水素ラジカルを照射する前の温度を１２０℃に代えて２００℃としたこと、及び、炉内の水素ガス除去後の加熱温度を１４５℃に代えて２２５℃としたことを除き、工程（ａ１）と同様にして、はんだ粒子を形成し、工程（ｂ２）で使用する、凹部に導電粒子（はんだ粒子）が配置された基体を用意した。 [Step (a4): Preparation and arrangement of solder particles (type: F2, average particle diameter: 4.0 μm)]
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.
　別途同様の操作ではんだ粒子を作製し、得られたはんだ粒子を、基体の凹部の裏側をタップすることで凹部より回収した。はんだ粒子は表面の一部に平面部を有し、はんだ粒子の直径Ａに対する平面部の直径Ｂの比（Ｂ／Ａ）が０．３５であることを確認した。また、はんだ粒子の投影像に外接する四角形を二対の平行線により作成したところ、対向する辺間の距離をＸ及びＹ（但しＹ＜Ｘ）としたときに、Ｙ／Ｘが０．９３であることを確認した。また、はんだ粒子の平均粒子径及び粒子径のＣ．Ｖ．値を測定したところ、平均粒子径は４．０μｍであり、粒子径のＣ．Ｖ．値は７．９％であった。なお、はんだ粒子の平均粒子径、Ｂ／Ａ、Ｙ／Ｘは、工程（ｂ）において作製した粒子転写層を、１０ｃｍ×１０ｃｍに切り出し、はんだ粒子が配置されている面にＰｔスパッタを施した後、３００個のはんだ粒子をＳＥＭ観察して測定された値である。 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. When the value was measured, the average particle size was 4.0 μm, and the particle size C.I. V. The value was 7.9%. For the average particle diameters of the solder particles, B / A and Y / X, 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.
［工程（ａ５）：導電粒子（種類：Ｆ３、平均粒子径：３．９μｍ）の用意及び配置］
　導電粒子として、プラスチック（架橋ポリスチレン）からなる核（粒子）の表面に、厚さ０．１５μｍのニッケル層が形成されてなる導電粒子（種類：Ｆ３、平均粒子径：３．９μｍ、粒子径のＣ．Ｖ．値：３．０％、比重：２．７）を用意し、これを基体（Ａ）の凹部が形成されている面上に配置した。次いで、基体（Ａ）の凹部が形成されている面を微粘着ローラーで擦ることで余分な導電粒子を取り除き、凹部内のみに導電粒子を配置した。導電粒子の平均粒子径及び粒子径のＣ．Ｖ．値は、後述する工程（ｂ）において作製した粒子転写層を、１０ｃｍ×１０ｃｍに切り出し、導電粒子が配置されている面にＰｔスパッタを施した後、３００個の導電粒子をＳＥＭ観察して測定された値である。 [Step (a5): Preparation and arrangement of conductive particles (type: F3, average particle diameter: 3.9 μm)]
As conductive particles, conductive particles (type: F3, average particle diameter: 3.9 μm, particle diameter) in which a nickel layer having a thickness of 0.15 μm is formed on the surface of a nucleus (particle) made of plastic (crosslinked polystyrene). 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. Next, 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. C.I. of average particle diameter and particle diameter of conductive particles. V. The value is measured by cutting out the particle transfer layer produced in the step (b) described later into a size of 10 cm × 10 cm, applying Pt sputtering to the surface on which the conductive particles are arranged, and then observing 300 conductive particles by SEM. It is the value that was made.
（工程（ｂ）：転写工程）
［工程（ｂ１）：第１の接着剤層の作製］
　表１にＸ１又はＸ２として示す成分を表１に示す配合量（単位：質量部、固形分量）で有機溶媒（２－ブタノン）と共に混合し、樹脂溶液を得た。次いで、この樹脂溶液をシリコーン離型処理された厚さ３８μｍのＰＥＴフィルムに塗布し、６０℃で３分間熱風乾燥することによって、表２～４に示す厚さの第１の接着剤層をＰＥＴフィルム上に作製した。 (Step (b): Transfer step)
[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 μm-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.
［工程（ｂ２）：導電粒子の転写］
　工程（ｂ１）で作製した、ＰＥＴフィルム上に形成された上記第１の接着剤層と、工程（ａ）で作製した、凹部に導電粒子が配置された基体とを向かい合わせて配置し、第１の接着剤層に導電粒子を転写させた。これにより、粒子転写層を得た。 [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.
（工程ｃ：積層工程）
［工程（ｃ１）：第２の接着剤層の作製］
　表１にＸ１又はＸ２として示す成分を表１に示す配合量（単位：質量部、固形分量）で有機溶媒（２－ブタノン）と共に混合し、樹脂溶液を得た。次いで、この樹脂溶液をシリコーン離型処理された厚さ５０μｍのＰＥＴフィルムに塗布し、６０℃で３分間熱風乾燥することによって、表２～４に示す厚さの第２の接着剤層をＰＥＴフィルム上に作製した。 (Step c: Laminating step)
[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 μm 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.
［工程（ｃ２）：第２の接着剤層の積層］
　工程（ｂ）で作製した粒子転写層と、工程（ｃ１）で作製した第２の接着剤層とを、５０℃の温度をかけながら貼り合わせた。これにより、異方導電性接着剤フィルムを得た。異方導電性接着剤フィルムの厚さ、及び、導電粒子の平均粒子径に対する異方導電性接着剤フィルムの厚さの比ｒは表２～４に示す。 [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.
（接着剤フィルム表面から導電粒子までの距離の測定）
　異方導電性接着剤フィルムをエポキシ樹脂系注型樹脂（リファインテック株式会社製、商品名：エポマウント）を用いて注型した後、導電性接着剤フィルムの断面を切り出した。その後、ニコンソリューションズ社製の金属ＦＰＤ／ＬＳＩ検査顕微鏡Ｌ３００ＮＤを用いて断面を観察し、１０箇所で異方導電性接着剤フィルムにおける第１の接着剤層側の表面から導電粒子の表面までの最短距離及び異方導電性接着剤フィルムにおける第２の接着剤層側の表面から導電粒子の表面までの最短距離を測定し、１０箇所の測定値の平均をそれぞれ最短距離ｄ１１及び最短距離ｄ２１を測定した。結果を表２～４に示す。 (Measurement of the distance from the surface of the adhesive film to the conductive particles)
After casting the anisotropic conductive adhesive film with an epoxy resin-based casting resin (manufactured by Refine Tech Co., Ltd., trade name: Epomount), a cross section of the conductive adhesive film was cut out. After that, the cross section was observed using a metal FPD / LSI inspection microscope L300ND manufactured by Nikon Solutions, and the shortest distance from the surface on the first adhesive layer side of the anisotropic conductive adhesive film to the surface of the conductive particles at 10 points. Distance and the shortest distance from the surface on the second adhesive layer side of the anisotropic conductive adhesive film to the surface of the conductive particles are measured, and the average of the measured values at 10 points is measured as the shortest distance d11 and the shortest distance d21, respectively. did. The results are shown in Tables 2-4.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
＜評価＞
（異方導電性接着剤フィルムの硬化率の測定）
　実施例１～８及び比較例１～６の各異方導電性接着剤フィルムについて、パーキンエルマー社製の示差走査熱量計（商品名：ＤＳＣ　Ｑ１０００）を用いて窒素（Ｎ２）雰囲気下、１０℃／分の昇温速度でＤＳＣ測定を実施し、５０℃から１３０℃まで加熱したときの発熱量ＱＡ、５０℃から１６０℃まで加熱したときの発熱量ＱＢ、５０℃から２１０℃まで加熱したときの発熱量ＱＣ及び５０℃から３００℃まで加熱したときの発熱量ＱＤを求めた。いずれの異方導電性接着剤フィルムにおいても、３００℃以上の温度での発熱量の上昇が見られなかった（ＤＳＣ曲線の微分曲線（ＤＤＳＣ曲線）の変化率が０．０１［Ｗ・ｇ℃］以下であった）ことから、３００℃において完全に硬化している（硬化率１００％）と判断した。得られた発熱量ＱＡ、ＱＢ、ＱＣ及びＱＤに基づき、１３０℃での硬化率Ａ（ＱＡ／ＱＤ×１００）、１６０℃での硬化率Ｂ（ＱＢ／ＱＤ×１００）、２１０℃での硬化率Ｃ（ＱＣ／ＱＤ×１００）をそれぞれ求めた。結果を表５及び表６に示す。 <Evaluation>
(Measurement of curing rate of anisotropic conductive adhesive film)
For each anisotropic conductive adhesive film of Examples 1 to 8 and Comparative Examples 1 to 6, a differential scanning calorimeter (trade name: DSC Q1000) manufactured by PerkinElmer Co., Ltd. was used in a nitrogen (N 2 ) atmosphere, and 10 DSC measurement was performed at a heating rate of ° C / min, and the calorific value QA when heated from 50 ° C to 130 ° C , the calorific value QB when heated from 50 ° C to 160 ° C , and from 50 ° C to 210 ° C. 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%). Based on the obtained calorific value Q A , Q B , Q C and Q D , the curing rate A at 130 ° C (Q A / Q D × 100) and the curing rate B at 160 ° C (Q B / Q D ×) 100) and the curing rate C (QC / QD × 100) at 210 ° C. were determined, respectively. The results are shown in Tables 5 and 6.
（異方導電性接着剤フィルム中の導電粒子の単分散率の測定）
　金属顕微鏡を用いて、２００倍の倍率で実施例１～８及び比較例１～６の異方導電性接着剤フィルムを第１の接着剤層側から観察し、異方導電性接着剤フィルム中の導電粒子数を実測し、下記式にしたがって導電粒子の単分散率を求めた。実施例１～８及び比較例１～６の異方導電性接着剤フィルム中の導電粒子の単分散率は、９８％であった。
単分散率（％）＝（２５００μｍ２中の単分散状態の導電粒子数／２５００μｍ２中の導電粒子数）×１００ (Measurement of monodispersity of conductive particles in anisotropic conductive adhesive film)
Using a metallurgical microscope, the anisotropic conductive adhesive films of Examples 1 to 8 and Comparative Examples 1 to 6 were observed from the first adhesive layer side at a magnification of 200 times, and were found in the anisotropic conductive adhesive film. The number of conductive particles was actually measured, and the monodisperse rate of the conductive particles was determined according to the following formula. The monodispersity of the conductive particles in the anisotropic conductive adhesive films of Examples 1 to 8 and Comparative Examples 1 to 6 was 98%.
Single dispersion rate (%) = (number of conductive particles in a monodisperse state in 2500 μm 2 / number of conductive particles in 2500 μm 2 ) × 100
（接続抵抗及び絶縁抵抗の評価）
［回路部材の準備］
　第１の回路部材として、無アルカリガラス基板（ＯＡ－１１、日本電気硝子株式会社製、外形：７６ｍｍ×２８ｍｍ、厚さ：０．３ｍｍ）の表面に、Ｃｒ（２０ｎｍ）／Ａｕ（２００ｎｍ）の電極（電極サイズ２２μｍ×２２μｍ、電極間スペース：８μｍ）を形成した電極付き基板（Ａ）を準備した。第２の回路部材として、バンプ電極を配列したサファイアチップ（外形：０．５ｍｍ×０．５ｍｍ、厚さ：０．２ｍｍ、バンプ電極の大きさ：２０μｍ×２０μｍ、バンプ電極間スペース：１０μｍ、バンプ電極厚さ：１．５μｍ）を準備した。 (Evaluation of connection resistance and insulation resistance)
[Preparation of circuit members]
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 μm × 22 μm, space between electrodes: 8 μm) was prepared. As the second circuit member, 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 μm × 20 μm, space between bump electrodes: 10 μm, bump Electrode thickness: 1.5 μm) was prepared.
［接続構造体（Ａ）の作製］
　実施例１～８及び比較例１～６の各異方導電性接着剤フィルムを用いて接続構造体（Ａ）の作製を行った。具体的には、まず、異方導電性接着剤フィルムを第１の回路部材上に配置した。次に、セラミックヒータからなるステージとツール（８ｍｍ×５０ｍｍ）とから構成される熱圧着装置（ＬＤ－０６、株式会社大橋製作所製）を用いて、５０℃、０．９８ＭＰａ（１０ｋｇｆ／ｃｍ２）の条件で２秒間加熱及び加圧して、第１の回路部材に異方導電性接着剤フィルムを貼り付け、異方導電性接着剤フィルムの第１の回路部材側とは反対側の離型フィルム（ＰＥＴフィルム）を剥離した。次いで、第１の回路部材のバンプ電極と第２の回路部材の回路電極との位置合わせを行った後、３０℃に加熱した台座上にて温度５０℃、圧力１ＭＰａにて加熱・加圧を開始し、加圧力を略一定（１ＭＰａ）に保持したまま１℃／秒の条件で１６０℃又は２３０℃まで昇温することで、異方導電性接着剤フィルムを第２の回路部材に貼り付けて接続構造体（Ａ）を作製した。なお、温度は異方導電性接着剤フィルムの実測最高到達温度、圧力は第２の回路部材のチップ面積に対して算出した値を示す。実施例１～７及び比較例１～６では昇温到達温度を１６０℃とし、実施例８では昇温到達温度を２３０℃とした。 [Preparation of connection structure (A)]
The 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 ). 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). The 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. In Examples 1 to 7 and Comparative Examples 1 to 6, the temperature rise reached was 160 ° C., and in Example 8, the temperature rise reached 230 ° C.
［接続抵抗の評価］
　四端子測定法にて実施し、接続構造体（Ａ）の作製直後及び温度８５℃湿度８５％ＲＨの高温高湿槽にて２５０時間処理した後、４箇所で測定した接続抵抗値の平均値を用いて接続抵抗を評価した。電流発生装置としてエーディーシー製の６２４０Ｂ（商品名）を用い、デジタルマルチメーターはエーディーシー製の７４６１Ａ（商品名）を用いた。接続抵抗が０．２Ω未満である場合を「Ｓ」判定として、接続抵抗が０．２Ω以上０．５Ω未満である場合を「Ａ」判定として、接続抵抗が０．５Ω以上である場合を「Ｄ」判定とした。結果を表５及び表６に示す。 [Evaluation of 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. When the connection resistance is less than 0.2Ω, it is judged as "S", when the connection resistance is 0.2Ω or more and less than 0.5Ω, it is judged as "A", and when the connection resistance is 0.5Ω or more, it is judged as "A". It was judged as "D". The results are shown in Tables 5 and 6.
［絶縁抵抗の評価］
　接続構造体（Ａ）の製作直後及び温度８５℃湿度８５％ＲＨの高温高湿槽にて２５０時間処理した後、４か所で測定した絶縁抵抗値の最小値を用いて絶縁抵抗を評価した。絶縁抵抗計は日置電機製のＳＭ７１２０（商品名）を用いた。絶縁抵抗値が１．０×１０１０Ω以上である場合を「Ｓ」判定とし、絶縁抵抗値が１．０×１０９Ω以上１．０×１０１０Ω未満である場合を「Ａ」判定とし、絶縁抵抗値が１．０×１０９Ω未満である場合を「Ｄ」判定として評価した。結果を表５及び表６に示す。 [Evaluation of insulation resistance]
Immediately after the 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 Ω or more, it is judged as “S”, and when the insulation resistance value is 1.0 × 10 9 Ω or more and less than 1.0 × 10 10 Ω, it is judged as “A”. When the insulation resistance value was less than 1.0 × 109 Ω, it was evaluated as “D”. The results are shown in Tables 5 and 6.
（粒子捕捉率の評価）
［接続構造体（Ｂ）の作製］
　実施例１～８及び比較例１～６の各異方導電性接着剤フィルムを用いて接続構造体（Ｂ）の作製を行った。接続構造体（Ｂ）の作製は、第１の回路部材として、無アルカリガラス基板（ＯＡ－１１、日本電気硝子株式会社製、外形：７６ｍｍ×２８ｍｍ、厚さ：０．３ｍｍ）の表面に、ＩＴＯ（２２０ｎｍ）の電極（電極サイズ２２μｍ×２２μｍ、電極間スペース：８μｍ）を形成した電極付き基板（Ｂ）を準備し、電極付き基板（Ａ）に代えて、電極付き基板（Ｂ）を用いたこと以外は、接続構造体（Ａ）の作製と同様にして行った。 (Evaluation of particle capture rate)
[Preparation of connection structure (B)]
The 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 μm × 22 μm, space between electrodes: 8 μm) 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.
［粒子捕捉率の評価］
　接続構造体（Ｂ）の接続箇所を電極付き基板（Ｂ）側からニコンソリューションズ社製の金属ＦＰＤ／ＬＳＩ検査顕微鏡Ｌ３００ＮＤを用いて観察し、２５箇所の接続箇所において、捕捉された導電粒子数（ＩＴＯ電極とバンプ電極との間（バンプ電極上）に捕捉された導電粒子数）を計測し、１バンプ電極（電極面積：２０μｍ×２０μｍ＝４００μｍ）あたりに捕捉された導電粒子数の平均値（平均捕捉粒子数）を求めた。得られた平均捕捉粒子数と、異方導電性接着剤フィルム中の導電粒子の密度（２９０００個／ｍｍ２）とを用いて、下記式に基づき、電極間に捕捉された導電粒子の捕捉率を算出した。導電粒子の捕捉率が７０％以上である場合を「Ｓ」判定とし、導電粒子の捕捉率が６０％以上７０％未満である場合を「Ａ」判定とし、導電粒子の捕捉率が５０％以上６０％未満である場合を「Ｂ」判定とし、導電粒子の捕捉率が５０％未満である場合を「Ｄ」判定として評価した。結果を表５及び表６に示す。
導電粒子の捕捉率（％）＝（平均捕捉粒子数／（バンプ電極面積×異方導電性接着剤フィルム中の導電粒子の密度））×１００ [Evaluation of particle capture rate]
The connection points of the connection structure (B) were observed from the electrode-attached substrate (B) side using a metal FPD / LSI inspection microscope L300ND manufactured by Nikon Solutions, and the number of conductive particles captured at the 25 connection points ( The number of conductive particles captured between the ITO electrode and the bump electrode (on the bump electrode) is measured, and the average value of the number of conductive particles captured per one bump electrode (electrode area: 20 μm × 20 μm = 400 μm) ( The average number of captured particles) was calculated. Using the obtained average number of captured particles and the density of conductive particles in the anisotropic conductive adhesive film (29000 / mm 2 ), the capture rate of the conductive particles captured between the electrodes is based on the following formula. Was calculated. When 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. When it was less than 60%, it was evaluated as "B", and when the capture rate of conductive particles was less than 50%, it was evaluated as "D". The results are shown in Tables 5 and 6.
Capturing rate of conductive particles (%) = (average number of captured particles / (bump electrode area x density of conductive particles in anisotropic conductive adhesive film)) x 100
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　１…接着剤フィルム、２…はんだ粒子、３…第１の接着剤層、４…第２の接着剤層、６…基体、７…凹部、１０…回路接続用接着剤フィルム、２１…第１の回路基板、２２…第１の電極（回路電極）、２３…第１の回路部材、２４…第２の回路基板、２５…第２の電極（バンプ電極）、２６…第２の回路部材、２７…接続部、３０…はんだ層、１００…接続構造体。 1 ... Adhesive film, 2 ... Solder particles, 3 ... First adhesive layer, 4 ... Second adhesive layer, 6 ... Base, 7 ... Recesses, 10 ... Circuit connection adhesive film, 21 ... First Circuit board, 22 ... first electrode (circuit electrode), 23 ... first circuit member, 24 ... second circuit board, 25 ... second electrode (bump electrode), 26 ... second circuit member, 27 ... Connection part, 30 ... Solder layer, 100 ... Connection structure.

Claims (10)

  1. 　熱硬化性の回路接続用接着剤フィルムであって、
    　平均粒子径が１～３０μｍであり、粒子径のＣ．Ｖ．値が２０％以下であるはんだ粒子を含有し、
    　前記はんだ粒子の平均粒子径に対する前記回路接続用接着剤フィルムの厚さの比が、１．０超１．５未満であり、
    　前記はんだ粒子の融点をＴｍ℃とすると、窒素雰囲気下、１０℃／分の昇温速度で加熱したときのＴｍ℃での硬化率が８０％以上である、回路接続用接着剤フィルム。     Thermosetting adhesive film for circuit connection
    The average particle size is 1 to 30 μm, and the particle size is C.I. V. Contains solder particles with a value of 20% or less,
    The ratio of the thickness of the circuit connecting adhesive film to the average particle diameter of the solder particles is more than 1.0 and less than 1.5.
    Assuming that the melting point of the solder particles is T m ° C, the adhesive film for circuit connection 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.
  2. 　重合性化合物と、熱重合開始剤とを含有する、請求項１に記載の回路接続用接着剤フィルム。 The circuit connection adhesive film according to claim 1, which contains a polymerizable compound and a thermal polymerization initiator.
  3. 　前記重合性化合物が、カチオン重合性化合物であり、前記熱重合開始剤が熱カチオン重合開始剤である、請求項２に記載の回路接続用接着剤フィルム。 The circuit connection adhesive film according to claim 2, wherein the polymerizable compound is a cationically polymerizable compound, and the thermal polymerization initiator is a thermal cationic polymerization initiator.
  4. 　前記重合性化合物が、脂環式エポキシ化合物及びオキセタン化合物からなる群より選択される少なくとも一種を含む、請求項３に記載の回路接続用接着剤フィルム。 The adhesive film for circuit connection according to claim 3, wherein the polymerizable compound contains at least one selected from the group consisting of an alicyclic epoxy compound and an oxetane compound.
  5. 　前記はんだ粒子の融点が、２８０℃以下である、請求項１～４のいずれか一項に記載の回路接続用接着剤フィルム。 The adhesive film for circuit connection according to any one of claims 1 to 4, wherein the solder particles have a melting point of 280 ° C. or lower.
  6. 　第１の電極を有する第１の回路部材と第２の電極を有する第２の回路部材とを接着すると共に、前記第１の電極と前記第２の電極とを互いに電気的に接続するために用いられ、
    　前記第１の電極の高さと前記第２の電極の高さの合計が、前記はんだ粒子の平均粒子径よりも小さい、請求項１～５のいずれか一項に記載の回路接続用接着剤フィルム。     In order to bond the first circuit member having the first electrode and the second circuit member having the second electrode, and to electrically connect the first electrode and the second electrode to each other. Used,
    The adhesive film for circuit connection according to any one of claims 1 to 5, wherein the sum of the height of the first electrode and the height of the second electrode is smaller than the average particle diameter of the solder particles. ..
  7. 　第１の電極を有する第１の回路部材と、前記第１の電極と電気的に接続される第２の電極を有する第２の回路部材と、前記第１の電極と前記第２の電極とをはんだ層を介して互いに電気的に接続し且つ前記第１の回路部材と前記第２の回路部材とを接着する接続部と、を備え、
    　前記接続部が、請求項１～６のいずれか一項に記載の回路接続用接着剤フィルムの硬化物を含む、接続構造体。     A first circuit member having a first electrode, a second circuit member having a second electrode electrically connected to the first electrode, the first electrode, and the second electrode. Provided with a connecting portion for electrically connecting the first circuit member to each other via a solder layer and adhering the first circuit member and the second circuit member.
    A connection structure in which the connection portion contains a cured product of the adhesive film for circuit connection according to any one of claims 1 to 6.
  8. 　前記第１の電極の高さと前記第２の電極の高さの合計が、前記はんだ粒子の平均粒子径よりも小さい、請求項７に記載の接続構造体。 The connection structure according to claim 7, wherein the sum of the height of the first electrode and the height of the second electrode is smaller than the average particle diameter of the solder particles.
  9. 　第１の電極を有する第１の回路部材の前記第１の電極が設けられている面と、第２の電極を有する第２の回路部材の前記第２の電極が設けられている面との間に、請求項１～６のいずれか一項に記載の回路接続用接着剤フィルムを配置することと、
    　前記第１の回路部材と前記回路接続用接着剤フィルムと前記第２の回路部材とを含む積層体を前記積層体の厚さ方向に押圧した状態で加熱することにより、前記第１の電極と前記第２の電極とをはんだ層を介して互いに電気的に接続し且つ前記第１の回路部材と前記第２の回路部材とを接着することと、を含む、接続構造体の製造方法。     A surface of the first circuit member having the first electrode provided with the first electrode and a surface of the second circuit member having the second electrode provided with the second electrode. The circuit connection adhesive film according to any one of claims 1 to 6 is placed between them.
    By heating the laminate including the first circuit member, the adhesive film for connecting the circuit, and the second circuit member in a state of being pressed in the thickness direction of the laminate, the first electrode can be obtained. A method for manufacturing a connection structure, comprising electrically connecting the second electrode to each other via a solder layer and adhering the first circuit member and the second circuit member to each other.
  10. 　前記第１の電極の高さと前記第２の電極の高さの合計が、前記はんだ粒子の平均粒子径よりも小さい、請求項９に記載の接続構造体の製造方法。 The method for manufacturing a connection structure according to claim 9, wherein the sum of the height of the first electrode and the height of the second electrode is smaller than the average particle diameter of the solder particles.
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