WO2020184636A1 - 回路接続用接着剤フィルム、回路接続構造体の製造方法及び接着剤フィルム収容セット - Google Patents

回路接続用接着剤フィルム、回路接続構造体の製造方法及び接着剤フィルム収容セット Download PDF

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Publication number
WO2020184636A1
WO2020184636A1 PCT/JP2020/010657 JP2020010657W WO2020184636A1 WO 2020184636 A1 WO2020184636 A1 WO 2020184636A1 JP 2020010657 W JP2020010657 W JP 2020010657W WO 2020184636 A1 WO2020184636 A1 WO 2020184636A1
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WIPO (PCT)
Prior art keywords
adhesive layer
circuit
adhesive
adhesive film
conductive particles
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PCT/JP2020/010657
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English (en)
French (fr)
Japanese (ja)
Inventor
伊藤　彰浩
友美子 大當
直 工藤
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日立化成株式会社
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Priority to JP2021505115A priority Critical patent/JPWO2020184636A1/ja
Priority to KR1020217031914A priority patent/KR20210141955A/ko
Priority to CN202080019596.3A priority patent/CN113574130A/zh
Publication of WO2020184636A1 publication Critical patent/WO2020184636A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

  • the present invention relates to an adhesive film for circuit connection, a method for manufacturing a circuit connection structure, and an adhesive film accommodating set.
  • circuit connection As an adhesive material for connecting a liquid crystal display and a tape carrier package (TCP), a flexible printed wiring board (FPC) and TCP, or a connection between FPC and a printed wiring board, conductive particles in an adhesive.
  • An adhesive film for circuit connection having an anisotropic conductivity in which is dispersed is used. Specifically, the circuit members are bonded to each other by the circuit connection portion formed of the circuit connection adhesive film, and the electrodes on the circuit members are electrically connected to each other via the conductive particles in the circuit connection portion. By doing so, a circuit connection structure is obtained.
  • the circuit connection adhesive film contains, for example, an adhesive component containing a thermosetting resin or the like and conductive particles to be blended as necessary, and adheres to a substrate such as a polyethylene terephthalate (PET) film. It is formed in the form of a film as an agent layer. Further, the adhesive film may be used in the state of a reel in which a film-like raw fabric is cut into a tape having a width suitable for the intended use, and the tape is wound around a winding core to form a winding body (for example, a patent). Reference 1).
  • PET polyethylene terephthalate
  • the present invention has been made to solve the above problems, and even when the circuit is connected by first attaching it to a flexible substrate, the circuit connection structure has excellent connection reliability between the opposing circuit members. It is an object of the present invention to provide an adhesive film for circuit connection from which a body can be obtained, a method for manufacturing a circuit connection structure using the same, and an adhesive film accommodating set.
  • the adhesive film for circuit connection on one side of the present invention includes a peelable support film, a first adhesive layer containing conductive particles provided on the support film, and the first adhesive layer.
  • a second adhesive layer is provided, and the thickness of the first adhesive layer is 0.1 to 1.0 times the average particle size of the conductive particles.
  • a circuit connection structure having excellent connection reliability between opposing circuit members can be obtained even when the circuit is connected by first attaching to the flexible substrate. ..
  • the first adhesive layer it is preferable that 90% or more of the conductive particles are separated from other conductive particles.
  • the first adhesive layer may consist of a cured product of the first curable composition, and the first curable composition may contain a radically polymerizable compound having a radically polymerizable group.
  • the second adhesive layer may consist of a second curable composition, and the second curable composition may contain a radically polymerizable compound having a radically polymerizable group.
  • the above-mentioned circuit connection bonding is performed between the first circuit member having the first electrode and the second circuit member having the second electrode.
  • a first adhesive layer and a second adhesive layer of the agent film are interposed, and the first circuit member and the second circuit member are heat-bonded to electrically attach the first electrode and the second electrode to each other. It is provided with a process of connecting to.
  • the first circuit member has a flexible substrate
  • the circuit connection adhesive film is in contact with the first circuit member
  • the second adhesive layer is in contact with the first circuit member. May be provided with a step of attaching to the first circuit member.
  • the adhesive film accommodating set on one side of the present invention includes the above-mentioned adhesive film for circuit connection and an accommodating member accommodating the adhesive film, and the accommodating member can visually recognize the inside of the accommodating member from the outside. It has a visible portion, and the transmittance of light having a wavelength of 365 nm in the visible portion is 10% or less.
  • a circuit connection adhesive capable of obtaining a circuit connection structure having excellent connection reliability between opposing circuit members even when the circuit is connected by first attaching to a flexible substrate.
  • a film, a method of manufacturing a circuit connection structure using the film, and an adhesive film accommodating set can be provided.
  • FIG. 1 It is a schematic cross-sectional view which shows one Embodiment of the adhesive film for circuit connection which concerns on this invention. It is a schematic cross-sectional view which shows the process of the manufacturing method of a circuit connection structure. It is a schematic cross-sectional view which shows the laminated body obtained through the process of FIG. It is a schematic cross-sectional view which shows the subsequent process of FIG. It is a schematic cross-sectional view which shows the circuit connection structure obtained through the process of FIG. It is the schematic which shows the manufacturing process of the adhesive film for circuit connection shown in FIG. It is a schematic diagram which shows the state of the magnetic field application process. It is a schematic cross-sectional view which shows the state of the adhesive film for circuit connection after going through a magnetic field application process and a drying process. It is a schematic cross-sectional view which shows the laminating process which follows FIG. It is a perspective view which shows one Embodiment of the adhesive film accommodating set which concerns on this invention.
  • (meth) acrylate means at least one of acrylate and the corresponding methacrylate. The same is true for other similar expressions such as "(meth) acryloyl”.
  • FIG. 1 is a schematic cross-sectional view showing an adhesive film for circuit connection according to an embodiment.
  • the circuit connection adhesive film 11 (hereinafter, also simply referred to as “adhesive film 11”) has a peelable support film 12 and a first adhesive provided on the support film 12. It includes an agent layer 13 and a second adhesive layer 14 laminated on the first adhesive layer 13.
  • the first adhesive layer 13 contains conductive particles P.
  • the adhesive film 11 is an anisotropically conductive adhesive film having anisotropic conductivity.
  • the adhesive film 11 has a first adhesive layer and a second adhesive layer interposed between the first circuit member having the first electrode and the second circuit member having the second electrode. , The first circuit member and the second circuit member are heat-bonded to electrically connect the first electrode and the second electrode to each other.
  • circuit connection adhesive film 11 when the circuit member to be connected has a flexible substrate, the circuit connection adhesive film 11 is first contacted with the circuit connection adhesive film so that the second adhesive layer is in contact with the first circuit member. Can be attached to the circuit member of.
  • the thickness of the first adhesive layer 13 is 0.1 to 1.0 times, more preferably 0.1 to 0.7 times, the average particle size of the conductive particles P. Good. Further, in the first adhesive layer 13, 90% or more of the conductive particles P may be in a state of being separated from other conductive particles.
  • the ratio of the melt viscosity X of the first adhesive layer 13 to the minimum melt viscosity Y of the second adhesive layer 14 at a temperature Ty at which the second adhesive layer 14 exhibits the lowest melt viscosity Y. (X / Y) may be 10 or more.
  • the melt viscosity ratio (X / Y) is preferably 10 or more, more preferably 20 or more, still more preferably 50 or more, and particularly preferably 50 or more, from the viewpoint of improving the adhesion to the circuit member. Is 100 or more.
  • the ratio of melt viscosity (X / Y) may be 10000 or less, 5000 or less, or 1000 or less from the viewpoint of wettability to circuit members. From these viewpoints, the melt viscosity ratio (X / Y) may be 10 to 10000, 20 to 5000, 50 to 5000, or 100 to 1000.
  • the melt viscosity X and the minimum melt viscosity Y first show the minimum melt viscosity Y of the second adhesive layer (and the second adhesive layer shows the minimum melt viscosity Y) by measuring the melt viscosity of the second adhesive layer. After determining the temperature Ty), it can be confirmed by determining the melt viscosity X of the first adhesive layer at the temperature Ty by measuring the melt viscosity of the first adhesive layer. The melt viscosity can also be measured after the adhesive film is obtained.
  • the support film 12 is made of, for example, polyethylene terephthalate (PET), polyethylene, polypropylene, or the like.
  • PET polyethylene terephthalate
  • the support film 12 may contain any filler. Further, the surface of the support film 12 may be subjected to a mold release treatment, a plasma treatment, or the like.
  • the support film 12 can be peeled off after transferring the first adhesive layer and the second adhesive layer to the circuit member.
  • the first adhesive layer comprises, for example, a cured product of the first curable composition.
  • the first curable composition may be a photocurable composition, a thermosetting composition, or a mixture of a photocurable composition and a thermosetting composition.
  • the first curable composition is, for example, (A) a polymerizable compound (hereinafter, also referred to as “(A) component”), (B) a polymerization initiator (hereinafter, also referred to as “(B) component”). , And (C) conductive particles (hereinafter, also referred to as “(C) component”).
  • the first curable composition When the first curable composition is a photocurable composition, the first curable composition contains a photopolymerization initiator as the component (B), and the first curable composition is a thermosetting composition. In the case of a product, the first curable composition contains a thermosetting initiator as the component (B).
  • the component (A) is polymerized by irradiating or heating the layer made of the first curable composition with light to obtain the first curable composition. Obtained by curing. That is, the first adhesive layer may consist of conductive particles and an adhesive component obtained by photocuring the first curable composition.
  • the first adhesive layer may be a cured product obtained by completely curing the first curable composition, or may be a cured product obtained by partially curing the first curable composition. .. That is, when the first curable composition contains the component (A) and the component (B), the adhesive component may contain the unreacted component (A) and the component (B). You don't have to.
  • the first adhesive layer may be made of a resin composition other than the cured product of the curable composition.
  • the first adhesive layer may consist of a resin composition containing a resin component such as a phenoxy resin such as PKHC, a polyester urethane resin, a polyurethane resin, or an acrylic rubber.
  • the melt viscosity at a temperature (for example, 100 ° C.) at which the second adhesive layer exhibits the minimum melt viscosity can be adjusted to about 100,000 to 10,000,000,000 Pa ⁇ s, and the ratio of the melt viscosity (for example, 100,000 Pa ⁇ s) can be adjusted.
  • X / Y) can be 10 or more.
  • the component (A) is, for example, a compound polymerized by a radical, cation or anion generated by a polymerization initiator (photopolymerization initiator or thermal polymerization initiator) by irradiation or heating with light (for example, ultraviolet light).
  • the component (A) may be any of a monomer, an oligomer or a polymer.
  • one kind of compound may be used alone, or a plurality of kinds of compounds may be used in combination.
  • the component (A) has at least one polymerizable group.
  • the polymerizable group is, for example, a group containing a polymerizable unsaturated double bond (ethylenically unsaturated bond).
  • the polymerizable radical further improves the viewpoint that the desired melt viscosity can be easily obtained, the viewpoint that peeling between the circuit member and the circuit connection portion is less likely to occur in a high temperature and high humidity environment, and the effect of reducing the connection resistance. From the viewpoint of being more excellent in connection reliability, a radically polymerizable group that reacts with radicals is preferable. That is, the component (A) is preferably a radically polymerizable compound.
  • Examples of the radically polymerizable group include a vinyl group, an allyl group, a styryl group, an alkenyl group, an alkenylene group, a (meth) acryloyl group, a maleimide group and the like.
  • the number of polymerizable groups contained in the component (A) may be 2 or more from the viewpoint that a desired melt viscosity can be easily obtained after polymerization and from the viewpoint of easily controlling the physical properties of the resin after curing, and at the time of polymerization. It may be 10 or less from the viewpoint of suppressing the curing shrinkage of. Further, in order to balance the crosslink density and the curing shrinkage, a polymerizable compound having a number of polymerizable groups within the above range may be used, and then a polymerizable compound outside the above range may be additionally used.
  • component (A) examples include (meth) acrylate compound, maleimide compound, vinyl ether compound, allyl compound, styrene derivative, acrylamide derivative, nadiimide derivative, natural rubber, isoprene rubber, butyl rubber, nitrile rubber, butadiene rubber, and styrene-.
  • examples thereof include butadiene rubber, acrylonitrile-butadiene rubber, and carboxylated nitrile rubber.
  • Examples of the (meth) acrylate compound include epoxy (meth) acrylate, (poly) urethane (meth) acrylate, methyl (meth) acrylate, polyether (meth) acrylate, polyester (meth) acrylate, polybutadiene (meth) acrylate, and silicone acrylate.
  • Maleimide compounds include 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-toluylene bismaleimide.
  • N, N'-4,4-biphenylene bismaleimide N, N'-4,4- (3,3'-dimethyl-biphenylene) bismaleimide, N, N'-4,4- (3,3' -Dimethyldiphenylmethane) bismaleimide, N, N'-4,4- (3,3'-diethyldiphenylmethane) bismaleimide, N, N'-4,4-diphenylmethane bismaleimide, N, N'-4,4- Diphenylpropane bismaleimide, N, N'-4,4-diphenyl ether bismaleimide, N, N'-3,3-diphenylsulfone bismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-s-butyl-4-8 (4-maleimidephenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidephenoxy) phenyl) de
  • vinyl ether compound examples include diethylene glycol divinyl ether, dipropylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylolpropane trivinyl ether.
  • allyl compound examples include 1,3-diallyl phthalate, 1,2-diallyl phthalate, and triallyl isocyanurate.
  • the component (A) is preferably a (meth) acrylate compound from the viewpoint that a desired melt viscosity can be easily obtained and compounds having various structures can be selected and easily obtained.
  • the component (A) may be a (poly) urethane (meth) acrylate compound (urethane (meth) acrylate compound or polyurethane (meth) acrylate compound) from the viewpoint of obtaining more excellent adhesive properties.
  • the component (A) may be a (meth) acrylate compound having a high Tg skeleton such as a dicyclopentadiene skeleton from the viewpoint of obtaining more excellent adhesive properties.
  • the component (A) is an acrylic resin or a phenoxy resin from the viewpoint of easily obtaining the desired melt viscosity and from the viewpoint of balancing the crosslink density and the curing shrinkage, further reducing the connection resistance, and improving the connection reliability.
  • a compound for example, polyurethane (meth) acrylate) in which a polymerizable group such as a vinyl group, an allyl group, or a (meth) acryloyl group is introduced into the terminal or side chain of a thermoplastic resin such as a polyurethane resin may be used.
  • the weight average molecular weight of the component (A) may be 3000 or more, 5000 or more, or 10,000 or more from the viewpoint of excellent balance between the crosslink density and the curing shrinkage. Further, the weight average molecular weight of the component (A) may be 1 million or less, 500,000 or less, or 250,000 or less from the viewpoint of excellent compatibility with other components.
  • the weight average molecular weight refers to a value measured from a gel permeation chromatograph (GPC) using a calibration curve using standard polystyrene according to the conditions described in Examples.
  • the component (A) preferably contains, as the (meth) acrylate compound, a radically polymerizable compound having a phosphoric acid ester structure represented by the following general formula (1).
  • a radically polymerizable compound having a phosphoric acid ester structure represented by the following general formula (1).
  • n represents an integer of 1 to 3
  • R represents a hydrogen atom or a methyl group.
  • the radically polymerizable compound having the above phosphoric acid ester structure can be obtained, for example, by reacting anhydrous phosphoric acid with 2-hydroxyethyl (meth) acrylate.
  • Specific examples of the radically polymerizable compound having a phosphoric acid ester structure include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate and the like.
  • the content of the component (A) is 5% by mass or more based on the total mass of the first curable composition from the viewpoint that the desired melt viscosity can be easily obtained and the desired cured physical properties can be easily obtained. It may be 10% by mass or more, and may be 20% by mass or more.
  • the content of the component (A) may be 90% by mass or less, 80% by mass or less, based on the total mass of the first curable composition, from the viewpoint of suppressing curing shrinkage during polymerization. It may be 70% by mass or less.
  • Component (B): Polymerization Initiator The component (B) is radically irradiated by irradiation with light having a wavelength in the range of 150 to 750 nm, preferably light having a wavelength in the range of 254 to 405 nm, and more preferably light having a wavelength in the range of 365 nm (for example, ultraviolet light).
  • a photopolymerization initiator that generates cations or anions photoradical polymerization initiator, photocationic polymerization initiator or photoanionic polymerization initiator
  • a thermal polymerization initiator that generates radicals, cations or anions by heat It may be a thermal radical polymerization initiator, a thermal cationic polymerization initiator or a thermal anion polymerization initiator.
  • the component (B) is a radical from the viewpoint that the desired melt viscosity can be easily obtained, the effect of reducing the connection resistance is further improved, the connection reliability is improved, and the curing at a low temperature in a short time becomes easier.
  • the first curable composition may contain both a photopolymerization initiator and a thermal polymerization initiator as the component (B).
  • the photoradical polymerization initiator is decomposed by light to generate free radicals. That is, the photoradical polymerization initiator is a compound that generates radicals by applying light energy from the outside.
  • the photoradical polymerization initiator include an oxime ester structure, a bisimidazole structure, an acrydin structure, an ⁇ -aminoalkylphenone structure, an aminobenzophenone structure, an N-phenylglycine structure, an acylphosphine oxide structure, a benzyl dimethyl ketal structure, and an ⁇ -hydroxy. Examples thereof include compounds having a structure such as an alkylphenone structure.
  • the photoradical polymerization initiator is selected from the group consisting of an oxime ester structure, an ⁇ -aminoalkylphenone structure and an acylphosphine oxide structure from the viewpoint that the desired melt viscosity can be easily obtained and the effect of reducing the connection resistance is excellent. It is preferable to have at least one kind of structure.
  • the compound having an oxime ester structure examples include 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime and 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl).
  • Oxime 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-o-benzoyloxime, 1,3-diphenylpropanthrion- 2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2-( o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) and the like.
  • the compound having an ⁇ -aminoalkylphenone structure include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1. -Morphorinophenyl) -butanone-1 and the like.
  • the compound having an acylphosphine oxide structure include bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl)-.
  • examples thereof include phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the thermal radical polymerization initiator decomposes by heat to generate free radicals. That is, the thermal radical polymerization initiator is a compound that generates radicals by applying thermal energy from the outside.
  • the thermal radical polymerization initiator can be arbitrarily selected from conventionally known organic peroxides and azo compounds.
  • an organic peroxide having a 1-minute half-life temperature of 90 to 175 ° C. and a weight average molecular weight of 180 to 1000 is preferably used from the viewpoint of stability, reactivity and compatibility. Be done. When the half-life temperature for 1 minute is in this range, the storage stability is further excellent, the radical polymerization property is sufficiently high, and curing can be performed in a short time.
  • organic peroxides include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl) peroxy.
  • azo compound examples include 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), and 2,2'-azobisisobutyro.
  • examples thereof include nitrile, 2,2'-azobis (2-methylbutyronitrile), 4,4'-azobis (4-cyanovalerolic acid), and 1,1'-azobis (1-cyclohexanecarbonitrile).
  • the content of the component (B) is 0.1% by mass or more based on the total mass of the first curable composition from the viewpoint of excellent quick-curing property and excellent effect of reducing connection resistance. It may be 0.5% by mass or more.
  • the content of the component (B) may be 15% by mass or less based on the total mass of the first curable composition from the viewpoint of improving storage stability and excellent effect of reducing connection resistance. It may be 10% by mass or less, and may be 5% by mass or less.
  • the first curable composition preferably contains at least one of a photopolymerization initiator and a thermal polymerization initiator as the component (B), and adheres for circuit connection. It is more preferable to contain a photopolymerization initiator from the viewpoint of facilitating the production of the agent film.
  • the component (C) is not particularly limited as long as it is a conductive particle, and is a metal particle made of a metal such as Au, Ag, Ni, Cu, or solder, a conductive carbon particle made of conductive carbon, or the like. It may be.
  • the component (C) may be a coated conductive particle containing a nucleus containing non-conductive glass, ceramic, plastic (polystyrene, etc.) and the like, and a coating layer containing the metal or conductive carbon and coating the nucleus. Good.
  • coated conductive particles including metal particles formed of a heat-meltable metal or a core containing plastic and a coating layer containing metal or conductive carbon and coating the core are preferably used.
  • the contact area between the electrodes and the component (C) is set when the electrodes are electrically connected to each other. It can be increased to further improve the conductivity between the electrodes.
  • the component (C) may be an insulating coated conductive particle containing the above-mentioned metal particles, conductive carbon particles, or coated conductive particles and an insulating material such as a resin and having an insulating layer covering the surface of the particles. Good.
  • the component (C) is an insulating coated conductive particle, even when the content of the component (C) is large, the surface of the particle is coated with a resin, so that a short circuit due to contact between the components (C) occurs. Occurrence can be suppressed, and the insulation between adjacent electrode circuits can be improved.
  • the component (C) one of the various conductive particles described above may be used alone or in combination of two or more.
  • the maximum particle size of the component (C) needs to be smaller than the minimum distance between the electrodes (the shortest distance between adjacent electrodes).
  • the maximum particle size of the component (C) may be 1.0 ⁇ m or more, 2.0 ⁇ m or more, or 2.5 ⁇ m or more from the viewpoint of excellent dispersibility and conductivity.
  • the maximum particle size of the component (C) may be 50 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity.
  • the particle size of 300 arbitrary conductive particles (pcs) is measured by observation using a scanning electron microscope (SEM), and the largest value obtained is the maximum particle size of the component (C).
  • SEM scanning electron microscope
  • the particle size of the component (C) is the diameter of a circle circumscribing the conductive particles in the SEM image.
  • the average particle size of the component (C) may be 1.0 ⁇ m or more, 2.0 ⁇ m or more, or 2.5 ⁇ m or more from the viewpoint of excellent dispersibility and conductivity.
  • the average particle size of the component (C) may be 50 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity.
  • the particle size of 300 arbitrary conductive particles (pcs) is measured by observation using a scanning electron microscope (SEM), and the average value of the obtained particle sizes is taken as the average particle size.
  • the component (C) is preferably uniformly dispersed.
  • Particle density of the component (C) in the first adhesive layer from the viewpoint of stable connection resistance is obtained, it may be at 100pcs / mm 2 or more, may be at 1000pcs / mm 2 or more, 2000pcs / mm 2 That may be the above.
  • Particle density of the component (C) in the first adhesive layer, from the viewpoint of improving the insulating property between adjacent electrodes may be at 100000pcs / mm 2 or less, may be at 50000pcs / mm 2 or less, 10000pcs It may be / mm 2 or less.
  • the content of the component (C) may be 0.1% by volume or more based on the total volume in the first adhesive layer from the viewpoint of further improving the conductivity, and is 1% by volume or more. It may be 5% by volume or more.
  • the content of the component (C) may be 50% by volume or less, 30% by volume or less, and 20% by volume based on the total volume in the first adhesive layer from the viewpoint of easily suppressing a short circuit. It may be less than or equal to%.
  • the content of the component (C) in the first curable composition (based on the total product of the first curable composition) may be the same as the above range.
  • the first curable composition may further contain other components other than the component (A), the component (B) and the component (C).
  • Other components include, for example, thermoplastic resins, coupling agents and fillers. These components may be contained in the first adhesive layer.
  • thermoplastic resin examples include phenoxy resin, polyester resin, polyamide resin, polyurethane resin, polyester urethane resin, acrylic rubber and the like.
  • the first curable composition contains a thermoplastic resin
  • the first adhesive layer can be easily formed.
  • the first curable composition contains a thermoplastic resin
  • the stress of the first adhesive layer generated at the time of curing of the first curable composition can be relieved.
  • the thermoplastic resin has a functional group such as a hydroxyl group, the adhesiveness of the first adhesive layer is likely to be improved.
  • the content of the thermoplastic resin may be, for example, 5% by mass or more and 80% by mass or less based on the total mass of the first curable composition.
  • 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, a silane compound such as tetraalkoxysilane, a tetraalkoxy titanate derivative and a polydialkyl. Examples thereof include titanate derivatives.
  • the adhesiveness can be further improved.
  • the content of the coupling agent may be, for example, 0.1% by mass or more and 20% by mass or less based on the total mass of the first curable composition.
  • the filler 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 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 fine particles may have a uniform structure or may have a core-shell type structure.
  • the maximum diameter of the filler is preferably less than the minimum particle size of the conductive particles.
  • the content of the filler may be, for example, 0.1% by volume or more and 50% by volume or less based on the total volume of the first curable composition.
  • the first curable composition may contain other additives such as softeners, accelerators, deterioration inhibitors, colorants, flame retardants, thixotropic agents and the like.
  • the content of these additives may be, for example, 0.1 to 10% by mass based on the total mass of the first curable composition. These additives may be contained in the first adhesive layer.
  • the first curable composition may contain a thermosetting resin in place of the components (A) and (B), or in addition to the components (A) and (B).
  • a thermosetting resin is a resin that is cured by heat and has at least one or more thermosetting groups.
  • a thermosetting resin is, for example, a compound that crosslinks by reacting with a curing agent by heat.
  • the thermosetting resin one kind of compound may be used alone, or a plurality of kinds of compounds may be used in combination.
  • thermosetting group is, for example, an epoxy group, an oxetane group, an isocyanate group, or the like from the viewpoint that the desired melt viscosity can be easily obtained and the effect of reducing the connection resistance is further improved and the connection reliability is improved. Good.
  • thermosetting resin examples include bisphenol type epoxy resin which is a reaction product of epichlorohydrin and bisphenol A, F, AD and the like, and epoxy which is a reaction product of epichlorohydrin and phenol novolac, cresol novolac and the like.
  • examples thereof include novolak resins, naphthalene-based epoxy resins having a skeleton containing a naphthalene ring, and epoxy resins such as various epoxy compounds having two or more glycidyl groups in one molecule such as glycidylamine and glycidyl ether.
  • the content of the thermosetting resin in the first curable composition is, for example, the total mass of the first curable composition. As a reference, it may be 20% by mass or more and 80% by mass or less.
  • the content of the thermosetting resin in the first curable composition is, for example, the total mass of the first curable composition. As a reference, it may be 30% by mass or more and 70% by mass or less.
  • the first curable composition may contain the above-mentioned curing agent for the thermosetting resin.
  • the curing agent for the thermosetting resin include a thermal radical generator, a thermal cation generator, and a thermal anion generator.
  • the content of the curing agent may be, for example, 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the thermosetting resin.
  • the first adhesive layer may contain components derived from the first curable composition such as unreacted component (A) and component (B).
  • the unreacted component (B) remains in the first adhesive layer during storage and transportation.
  • a part of the second curable composition in the second adhesive layer is cured, and the adhesive film is easily peeled off between the circuit member and the circuit connection portion in a high temperature and high humidity environment. It is presumed that problems such as a decrease in the resistance reduction effect will occur. Therefore, from the viewpoint of suppressing the occurrence of the above-mentioned defects, the content of the component (B) in the first adhesive layer may be 15% by mass or less based on the total mass of the first adhesive layer.
  • the content of the component (B) in the first adhesive layer may be 0.1% by mass or more based on the total mass of the first adhesive layer.
  • the melt viscosity X of the first adhesive layer at a temperature Ty at which the second adhesive layer exhibits the minimum melt viscosity Y may be 1000 Pa ⁇ s or more from the viewpoint of making peeling less likely to occur, and may be 10,000 Pa ⁇ s. It may be more than 50,000 Pa ⁇ s or more.
  • the melt viscosity X may be 1000000 Pa ⁇ s or less, 1000000 Pa ⁇ s or less, and 500000 Pa ⁇ s or less from the viewpoint of excellent wettability to the substrate.
  • the melt viscosity X can be adjusted by changing the composition of the first curable composition, changing the curing conditions of the first curable composition, and the like.
  • the thickness of the first adhesive layer may be 0.1 times or more the average particle size of the conductive particles from the viewpoint that the conductive particles can be easily captured between the electrodes and the connection resistance can be further reduced. It may be 2 times or more, and may be 0.3 times or more.
  • the thickness of the first adhesive layer 2 is the average of the conductive particles from the viewpoint that the conductive particles are more easily crushed when they are sandwiched between the electrodes facing each other during thermocompression bonding, and the connection resistance can be further reduced.
  • the particle size may be 1.0 times or less, 0.8 times or less, and 0.7 times or less. From these viewpoints, the thickness of the first adhesive layer may be 0.1 to 0.7 times the average particle size of the conductive particles, 0.2 to 0.8 times, and 0.
  • the thickness of the adhesive layer refers to the thickness of the adhesive layer located at the separated portion of the adjacent conductive particles.
  • the thickness of the first adhesive layer and the average particle size of the conductive particles satisfy the above relationship, for example, as shown in FIG. 1, a part of the conductive particles P in the first adhesive layer 13 However, it may protrude from the first adhesive layer 13 toward the second adhesive layer 14.
  • the boundary S between the first adhesive layer 13 and the second adhesive layer 14 is located at the separated portion of the adjacent conductive particles P.
  • the conductive particles P are not exposed on the surface of the first adhesive layer 13 opposite to the side of the second adhesive layer 14, and the surface on the opposite side may be a flat surface.
  • the thickness of the first adhesive layer may be appropriately set according to the height of the electrodes of the circuit member to be adhered.
  • the thickness of the first adhesive layer may be, for example, 0.5 ⁇ m or more and 20 ⁇ m or less.
  • the length of the exposed portion of the conductive particles may be, for example, 0.1 ⁇ m or more and 20 ⁇ m or less.
  • the thickness of the adhesive layer can be measured by the following method. The adhesive film is sandwiched between two sheets of glass (thickness: about 1 mm), 100 g of bisphenol A type epoxy resin (trade name: JER811, manufactured by Mitsubishi Chemical Co., Ltd.) and a curing agent (trade name: Epomount curing agent, Refine Tech). After casting with a resin composition consisting of 10 g (manufactured by Hitachi, Ltd.), cross-section polishing is performed using a polishing machine, and a scanning electron microscope (SEM, trade name: SE-8020, manufactured by Hitachi High-Tech Science Co., Ltd.) is used. Measure the thickness of each adhesive layer.
  • SEM scanning electron microscope
  • the second adhesive layer comprises, for example, a second curable composition.
  • the second curable composition contains, for example, (a) a polymerizable compound (hereinafter, also referred to as (a) component) and (b) a polymerization initiator (hereinafter, also referred to as (b) component).
  • the second curable composition may be a thermosetting composition containing a thermosetting initiator as a component (b), and may be a photocurable composition containing a photopolymerization initiator as a component (b). It may be a mixture of a thermosetting composition and a photocurable composition.
  • the second curable composition constituting the second adhesive layer is an uncured curable composition that can flow when connected to a circuit, and is, for example, an uncured curable composition.
  • the component (a) is, for example, a compound polymerized by a radical, cation or anion generated by a polymerization initiator (photopolymerization initiator or thermal polymerization initiator) by irradiation or heating with light (for example, ultraviolet light).
  • a polymerization initiator photopolymerization initiator or thermal polymerization initiator
  • light for example, ultraviolet light
  • the compound exemplified as the component (A) can be used.
  • the component (a) reacts with radicals from the viewpoint of facilitating connection at a low temperature for a short time and easily obtaining a desired melt viscosity, further improving the effect of reducing connection resistance, and improving connection reliability. It is preferably a radically polymerizable compound having a radically polymerizable group.
  • Examples of the preferred radically polymerizable compound in the component (a) and the combination of the preferred radically polymerizable compound are the same as those in the component (A).
  • the component (a) is a radically polymerizable compound
  • the component (B) in the first adhesive layer is a photoradical polymerization initiator, it is adhered by accommodating the adhesive film in an accommodating member described later. Curing of the second curable composition during storage or transportation of the agent film tends to be significantly suppressed.
  • the component (a) may be any of a monomer, an oligomer or a polymer.
  • the component (a) one kind of compound may be used alone, or a plurality of kinds of compounds may be used in combination.
  • the component (a) may be the same as or different from the component (A).
  • the content of the component (a) is 10% by mass based on the total mass of the second curable composition from the viewpoint that the crosslink density required for reducing the connection resistance and improving the connection reliability can be easily obtained. It may be more than 20% by mass, and may be 30% by mass or more.
  • the content of the component (a) may be 90% by mass or less based on the total mass of the second curable composition, from the viewpoint of suppressing curing shrinkage during polymerization and obtaining good reliability, 80% by mass. It may be 70% by mass or less, and may be 70% by mass or less.
  • Component (b): Polymerization initiator As the component (b), the same polymerization initiator as the polymerization initiator exemplified as the component (B) can be used.
  • the component (b) is preferably a radical polymerization initiator. Examples of the preferred radical polymerization initiator in the component (b) are the same as those in the component (B).
  • the content of the component (b) is 0.1% by mass or more based on the total mass of the second curable composition from the viewpoint of facilitating connection at low temperature for a short time and being more excellent in connection reliability. It may be 0.5% by mass or more, and may be 1% by mass or more. The content of the component (b) may be 30% by mass or less, 20% by mass or less, and 10% by mass or less based on the total mass of the second curable composition from the viewpoint of pot life. It may be.
  • the second curable composition may further contain a component (a) and other components other than the component (b).
  • other components include thermoplastic resins, coupling agents, fillers, softeners, accelerators, deterioration inhibitors, colorants, flame retardants, thixotropic agents and the like.
  • the details of the other components are the same as the details of the other components in the first adhesive layer.
  • the second curable composition may contain a thermosetting resin in place of the components (a) and (b), or in addition to the components (a) and (b).
  • the second curable composition may contain a curing agent used to cure the thermosetting resin.
  • the thermosetting resin and the curing agent the same thermosetting resin and the curing agent as the thermosetting resin and the curing agent exemplified as other components in the first curable composition can be used.
  • the content of the thermosetting resin in the second curable composition is, for example, the total mass of the second curable composition. As a reference, it may be 20% by mass or more and 80% by mass or less.
  • the content of the thermosetting resin in the second curable composition is, for example, the total mass of the second curable composition. As a reference, it may be 20% by mass or more and 80% by mass or less.
  • the content of the curing agent may be the same as the range described as the content of the curing agent in the first curable composition.
  • the content of the conductive particles in the second adhesive layer may be, for example, 1% by mass or less, or 0% by mass, based on the total mass of the second adhesive layer.
  • the second adhesive layer preferably does not contain conductive particles.
  • the minimum melt viscosity Y of the second adhesive layer may be 50 Pa ⁇ s or more, 100 Pa ⁇ s or more, or 300 Pa ⁇ s or more from the viewpoint of obtaining excellent blocking resistance.
  • the minimum melt viscosity Y may be 100,000 Pa ⁇ s or less, may be 10,000 Pa ⁇ s or less, or may be 5000 Pa ⁇ s or less, from the viewpoint of obtaining excellent filling property between electrodes (resin filling property). ..
  • the minimum melt viscosity Y can be adjusted by changing the composition of the second curable composition or the like.
  • the thickness of the second adhesive layer may be appropriately set according to the height of the electrodes of the circuit member to be adhered.
  • the thickness of the second adhesive layer may be 5 ⁇ m or more and 200 ⁇ m or less from the viewpoint that the space between the electrodes can be sufficiently filled to seal the electrodes and better reliability can be obtained. It may be.
  • the first adhesive layer side in the second adhesive layer The thickness of the second adhesive layer is the distance from the surface on the opposite side to the boundary S between the first adhesive layer and the second adhesive layer located at the separated portion of the adjacent conductive particles. ..
  • the ratio of the thickness of the first adhesive layer 2 to the thickness of the second adhesive layer determines the space between the electrodes. From the viewpoint that the electrode can be sufficiently filled and the electrode can be sealed and better reliability can be obtained, the number may be 1 or more, and may be 1000 or less.
  • the thickness of the adhesive film (the total thickness of all the layers constituting the adhesive film) may be, for example, 5 ⁇ m or more, and may be 200 ⁇ m or less.
  • the above-mentioned adhesive film for circuit connection includes a peelable support film and an adhesive layer containing an adhesive component and conductive particles provided on the support film, and the conductive particles are unevenly distributed on the support film side.
  • the adhesive layer is dispersed in a direction orthogonal to the thickness direction of the adhesive layer, and the adhesive layer is a cured product of the above-mentioned first curable composition in the thickness direction of the adhesive layer from the support film side. It may have a first region containing the first region and a second region containing the second curable composition described above.
  • the ranges of the first region and the second region in the thickness direction of the adhesive layer can be set in the same manner as the thicknesses of the first adhesive layer and the second adhesive layer described above, respectively.
  • the conductive particles can also be set in the same manner as described above.
  • circuit connection adhesive film of the present embodiment has been described above, the present invention is not limited to the above embodiment.
  • the method for manufacturing the circuit connection structure of the present embodiment is a second circuit provided with a first circuit member provided with a first circuit electrode and a second circuit electrode corresponding to the first circuit electrode. This is a method for manufacturing a circuit connection structure formed by connecting members via the circuit connection adhesive film of the present embodiment described above.
  • the method of the present embodiment includes, for example, the preparatory step of preparing the adhesive film for circuit connection of the present embodiment described above.
  • the circuit connection adhesive film is placed on the first circuit member so that the second adhesive layer side of the circuit connection adhesive film faces the surface of the first circuit member where the circuit electrode is provided. Laminating process and laminating
  • the second circuit member is arranged on the first circuit member on which the circuit connection adhesive film is laminated so that the first circuit electrode and the second circuit electrode face each other, and the circuit connection adhesive film is arranged.
  • a heating and pressurizing step of pressurizing the first circuit member and the second circuit member in the direction in which the first circuit electrode and the second circuit electrode face each other while heating. To be equipped.
  • the above-described circuit connection adhesive film of the present embodiment can be manufactured.
  • the method for producing the circuit connection adhesive film of the present embodiment is, for example, a preparation step for preparing the first adhesive layer described above (first preparation step) and a first preparation step described above on the first adhesive layer. It may include a laminating step of laminating the adhesive layer of 2.
  • the method for manufacturing the adhesive film for circuit connection may further include a preparation step (second preparation step) for preparing the second adhesive layer.
  • the first adhesive layer is prepared by forming the first adhesive layer on the support film to obtain the first adhesive film.
  • the component (A), the component (B) and the component (C), and other components added as needed are added to the organic solvent and dissolved by stirring and mixing, kneading and the like.
  • disperse to prepare a varnish composition are added onto the release-treated substrate using a knife coater, roll coater, applicator, comma coater, die coater, etc., and then the organic solvent is volatilized by heating to form the substrate.
  • the layer composed of the first curable composition is irradiated with light or heated to cure the first curable composition and form the first adhesive layer on the substrate (). Curing process).
  • the first adhesive film is obtained.
  • the organic solvent used for preparing the varnish composition preferably has the property of uniformly dissolving or dispersing each component, and for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, butyl acetate and the like. Can be mentioned. These organic solvents can be used alone or in combination of two or more. Stirring and mixing and kneading in the preparation of the varnish composition can be carried out by using, for example, a stirrer, a raft machine, a triple roll, a ball mill, a bead mill or a homodisper.
  • the support film is not particularly limited as long as it has heat resistance that can withstand the heating conditions when volatilizing the organic solvent when the first curable composition is cured by light, and the first curable film is curable.
  • the composition is cured by heating, there is no particular limitation as long as it has heat resistance that can withstand the heating conditions for volatilizing the organic solvent and the heating conditions for curing the first curable composition. ..
  • the supporting film examples include stretched polypropylene (OPP), polyethylene terephthalate (PET), polyethylene naphthalate, polyethylene isophthalate, polyvinylidene terephthalate, polyolefin, polyacetate, polycarbonate, polyvinylidene sulfate, polyamide, polyimide, cellulose, ethylene / acetic acid.
  • a base material for example, a film
  • polyethylene terephthalate can be preferably used.
  • the heating conditions for volatilizing the organic solvent from the varnish composition applied to the support film are preferably conditions in which the organic solvent volatilizes sufficiently.
  • the heating conditions may be, for example, 40 ° C. or higher and 120 ° C. or lower for 0.1 minute or longer and 10 minutes or shorter.
  • irradiation light for example, ultraviolet light
  • Light irradiation can be performed using, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like.
  • the amount of light irradiation may be adjusted so that the ratio of melt viscosity (X / Y) is 10 or more.
  • the amount of light irradiation may be, for example, the integrated light amount of light having a wavelength of 365 nm, which may be 100 mJ / cm 2 or more, 200 mJ / cm 2 or more, or 300 mJ / cm 2 or more.
  • the dose of light for example, an accumulated light quantity of the wavelength 365nm light, may be at 10000 mJ / cm 2 or less, may be at 5000 mJ / cm 2 or less, may be at 3000 mJ / cm 2 or less.
  • the larger the light irradiation amount (integrated light amount of light) the larger the melt viscosity X tends to be, and the larger the melt viscosity ratio (X / Y) tends to be.
  • the heating conditions in the curing step may be adjusted so that the melt viscosity ratio (X / Y) is 10 or more.
  • the heating conditions may be, for example, 30 ° C. or higher and 300 ° C. or lower for 0.1 minutes or more and 5000 minutes or less, and 50 ° C. or higher and 150 ° C. or lower for 0.1 minutes or longer and 3000 minutes or shorter.
  • the higher the heating temperature the larger the melt viscosity X tends to be, and the higher the melt viscosity ratio (X / Y) tends to be.
  • the longer the heating time the larger the melt viscosity X tends to be, and the melt viscosity ratio (X / Y) tends to be larger.
  • the second preparation step other than using the components (a) and (b) and other components added as needed, and not performing the curing step (no light irradiation and heating).
  • the base material the same base material as the above-mentioned support film can be used.
  • the second adhesive layer may be laminated on the first adhesive layer by laminating the first adhesive film and the second adhesive film, and the first adhesive may be laminated.
  • the first adhesive is formed by applying a varnish composition obtained by using the components (a) and (b) and other components added as needed on the layer and volatilizing the organic solvent.
  • a second adhesive layer may be laminated on the layer.
  • Examples of the method of adhering the first adhesive film and the second adhesive film include methods such as heat pressing, roll laminating, and vacuum laminating. Lamination may be performed, for example, under heating conditions of 0 to 80 ° C.
  • a circuit connection adhesive film in which 90% or more of the conductive particles P are separated from other conductive particles is used in the first adhesive layer, such a dispersed state is used.
  • the conductive particles P nickel-containing particles are preferably used from the viewpoint of carrying out dispersion by the magnetic field application step.
  • iron, cobalt, and nickel are ferromagnets and are known to be magnetized by an external magnetic field. Among them, the use of nickel is significant in that both conductivity and dispersibility by applying a magnetic field can be achieved. Is.
  • the surface layer of the conductive particles P may be a white metal noble metal such as gold or silver instead of nickel.
  • the surface of nickel may be coated with a precious metal such as Au.
  • a non-conductive glass, ceramic, plastic or the like coated with a conductive substance such as the metal may be used, and in this case as well, a nickel layer may be provided to form a multilayer structure.
  • the magnetism of nickel is affected by the phosphorus concentration contained in nickel plating, it is preferable to adjust the magnetism required for dispersion of the conductive particles P by a magnetic field in a timely manner.
  • the magnetism of the conductive particles P can be measured for saturation magnetization by, for example, a vibrating sample magnetmeter (VSM).
  • VSM vibrating sample magnetmeter
  • the saturation magnetization is preferably in the range of 5.0 emu / g to 50 emu / g in VSM measurement. When it is 5.0 emu / g or more, it becomes easy to sufficiently disperse the conductive particles P.
  • the magnetization of the conductive particles P does not become too large, the conduction of the conductive particles P in the thickness direction of the first adhesive layer 13 is suppressed, and the dispersibility of the conductive particles P becomes high. It tends to be higher.
  • the average particle size of the conductive particles P is preferably 1.0 ⁇ m or more and 10.0 ⁇ m or less.
  • the average particle size of the conductive particles P is 1.0 ⁇ m or more, the coating accuracy on the support film is high, and the conductive particles P can be easily dispersed in the first adhesive layer.
  • the average particle size of the conductive particles P is 10.0 ⁇ m or less, good insulation between adjacent circuit electrodes of the connecting structure tends to be obtained.
  • the average particle size of the conductive particles P is more preferably 2.0 ⁇ m or more, and further preferably 2.5 ⁇ m or more.
  • the average particle size of the conductive particles P is more preferably 8.5 ⁇ m or less, further preferably 7 ⁇ m or less. Even more preferably, it is 6.0 ⁇ m or less.
  • the blending amount of the conductive particles P is preferably 1 part by volume to 100 parts by volume with respect to 100 parts by volume of the components other than the conductive particles P in the first adhesive layer. From the viewpoint of preventing short-circuiting of adjacent circuit electrodes due to the excessive presence of the conductive particles P, the blending amount of the conductive particles P is more preferably 10 parts by volume to 50 parts by volume. Furthermore, to the extent the average particle diameter is less 1.0 ⁇ m or 10.0 ⁇ m of the conductive particles, it is preferred particle density of the conductive particles is 1000 / mm 2 or more 50000 / mm 2 or less. In this case, the dispersibility of the conductive particles P and the insulating property between the adjacent circuit electrodes can be more preferably compatible with each other.
  • FIG. 2 is a schematic cross-sectional view showing a laminating step in the method for manufacturing a connection structure of the present embodiment.
  • the second adhesive layer 14 side of the circuit connection adhesive film 11 faces the surface of the first circuit member 2 where the first circuit electrode 6 is provided.
  • the circuit connection adhesive film 11 is laminated on the first circuit member 2.
  • the second adhesive layer 14 is the first after or while the release film is peeled off. It can be laminated so as to be in close contact with the circuit member 2.
  • the first circuit member 2 has a circuit electrode 6 on the mounting surface 5a side of the main body 5.
  • Examples of the first circuit member 2 include a member having a flexible substrate such as COP, FCP, and polyimide.
  • Examples of the circuit electrode 6 include copper plated with a metal such as tin.
  • An insulating layer may be formed on the mounting surface 5a where the circuit electrode 6 is not formed.
  • a known laminator can be used as the laminating means.
  • Laminating conditions can be set as appropriate.
  • FIG. 3 is a schematic cross-sectional view showing a laminated body obtained through a laminating step.
  • FIG. 4 is a schematic cross-sectional view showing a heating and pressurizing step in the method for manufacturing the connection structure of the present embodiment.
  • the circuit connection adhesive film (second adhesive layer 14 and the first adhesive) is adhered so that the first circuit electrode 6 and the second circuit electrode 8 face each other.
  • the second circuit member 3 is arranged on the first circuit member 2 on which the agent layer 13) is laminated, and the circuit connection adhesive film (second adhesive layer 14 and first adhesive layer 13) is applied. While heating, the first circuit member 2 and the second circuit member 3 are pressurized in the direction in which the first circuit electrode 6 and the second circuit electrode 8 face each other.
  • the second circuit member 3 is, for example, a glass substrate or a plastic substrate whose circuit is formed of ITO, IZO, metal or the like used for a liquid crystal display, a ceramic wiring board, or the like. As shown in FIG. 4, the second circuit member 3 has a second circuit electrode 8 corresponding to the first circuit electrode 6 on the mounting surface 7a side of the main body 7.
  • the circuit electrode 8 has, for example, a rectangular shape in a plan view, and has a thickness of, for example, about 100 nm to 1000 nm.
  • the surface of the circuit electrode 8 is one selected from, for example, gold, silver, copper, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, indium tin oxide (ITO), and indium zinc oxide (IZO). It is composed of two or more kinds of materials.
  • the mounting surface 7a may also have an insulating layer formed on a portion where the circuit electrode 8 is not formed.
  • thermocompression bonding device can be used as the heating means.
  • the heating temperature of the circuit connection adhesive film (second adhesive layer 14 and first adhesive layer 13) is equal to or higher than the temperature at which polymerization active species are generated in the curing agent and the polymerization of the polymerization monomer is started. Is preferable.
  • This heating temperature is, for example, 80 ° C. to 200 ° C., preferably 100 ° C. to 180 ° C.
  • the heating time is, for example, 0.1 seconds to 30 seconds, preferably 1 second to 20 seconds.
  • the heating temperature is 80 ° C. or higher, a sufficient curing rate is likely to be obtained, and when the heating temperature is 200 ° C. or lower, unwanted side reactions are less likely to proceed.
  • the heating time is 0.1 seconds or more, the curing reaction is likely to proceed sufficiently, and when the heating time is 30 seconds or less, the productivity of the cured product is easily maintained, and undesired side reactions are less likely to proceed.
  • thermocompression bonding device can be used as the pressurizing means.
  • the pressure and time of pressurization can be set as appropriate.
  • FIG. 5 is a schematic cross-sectional view showing a circuit connection structure obtained through a heating and pressurizing step.
  • the adhesive components of the circuit connection adhesive film (second adhesive layer 14 and first adhesive layer 13) flow, and the first circuit electrode 6 and the second circuit electrode 8 flow.
  • the second adhesive layer and the first adhesive layer are cured in a state where the distance between the two and the conductive particles P is reduced.
  • the first circuit electrode 6 and the second circuit electrode 8 are electrically connected, and the adjacent circuit electrodes 6 and 6 are adjacent to each other and adjacent to each other.
  • a cured product 4 of the circuit connection adhesive film (second adhesive layer 14 and first adhesive layer 13) is formed in a state where the circuit electrodes 8 and 8 are electrically insulated from each other, and is shown in FIG.
  • the circuit connection structure 1 is obtained.
  • the first circuit electrode 6 and the second circuit electrode are formed by the cured product 4 of the circuit connection adhesive film (second adhesive layer 14 and first adhesive layer 13).
  • the time-dependent change of the distance from 8 can be sufficiently prevented, and the long-term reliability of the electrical characteristics can be ensured.
  • the cured product 4 of the circuit connection adhesive film (second adhesive layer 14 and first adhesive layer 13) has a first region 9 formed by curing the first adhesive layer 13 and a second region 9. It has a second region 10 formed by curing the adhesive layer 14 of the above.
  • the first region 9 is located on the second circuit member 3 side
  • the second region 10 is located on the first circuit member 2 side.
  • the conductive particles P are interposed between the first circuit electrode 6 and the second circuit electrode 8 in a state of being slightly flattened by crimping. As a result, an electrical connection between the first circuit electrode 6 and the second circuit electrode 8 is realized. Further, the conductive particles P are separated between the adjacent first circuit electrodes 6 and 6 and between the adjacent second circuit electrodes 8 and 8, and between the adjacent first circuit electrodes 6 and 6. And electrical insulation between the adjacent second circuit electrodes 8 and 8 is realized.
  • FIG. 6 is a schematic view showing a manufacturing process of the adhesive film for circuit connection shown in FIG.
  • the long support film 12 is conveyed at a predetermined speed by the feeding roller 21 and the winding roller 22.
  • a coater 23 for applying the adhesive paste W which is a material for forming the first adhesive layer 13, is arranged on the transport path of the support film 12, and the adhesive paste in which the conductive particles P are dispersed by the coater 23 is arranged. W is applied onto the support film 12 (coating step).
  • the thickness of the adhesive paste W applied on the support film 12 by the coater 23 varies from time to time depending on the proportion of the solvent contained in the resin composition, but is less than 1.6 times the average particle size of the conductive particles P. It is preferable that
  • the viscosity of the adhesive paste W can be varied depending on the application and coating method, but is usually preferably 10 mPa ⁇ s to 10000 mPa ⁇ s. From the viewpoint of suppressing separation of the compound in the adhesive paste W and improving compatibility, it is more preferably 50 mPa ⁇ s to 5000 mPa ⁇ s. Further, in order to improve the appearance of the circuit connection adhesive film 11, it is preferably 100 mPa ⁇ s to 3000 mPa ⁇ s.
  • the coating method of the adhesive paste W is not limited to the above, and a known method can be used.
  • the law etc. can be mentioned.
  • the bar coating method, the die coating method, the microgravure coating method and the like are suitable for producing the adhesive film 11 for circuit connection, and the microgravure coating method is particularly suitable from the viewpoint of the accuracy of the film thickness.
  • a pair of magnets 24 and 25 are arranged vertically facing each other so as to sandwich the support film 12.
  • the magnet 24 arranged on the upper side has an N pole and the magnet 25 arranged on the lower side has an S pole, and the magnet 24 is oriented substantially vertically toward the magnet 25.
  • a magnetic field is formed. Therefore, when the support film 12 is conveyed between the magnets 24 and 25, the conductive particles P in the adhesive paste W are magnetized, and the conductive particles P and P are separated from each other in the in-plane direction of the adhesive paste W by a repulsive force. A state is formed (magnetic field application step).
  • the adhesive paste W is dried by hot air or the like while the support film 12 passes between the magnets 24 and 25 (drying step).
  • the viscosity of the adhesive paste W is increased, and as shown in FIG. 8, 70% or more, preferably 90% or more of the conductive particles P are separated from the other adjacent conductive particles P.
  • the adhesive layer 13 of the above is formed on the support film 12.
  • the thickness of the adhesive paste W decreases due to the drying step, and as described above, the thickness of the adhesive paste W is set to less than 1.6 times the average particle size of the conductive particles P, so that the first method is performed.
  • the thickness of the adhesive layer 13 can be easily set to 0.6 times or more and less than 1.0 times the average particle size of the conductive particles P. Further, by using an adhesive paste (varnish) diluted with an organic solvent (for example, methyl ethyl ketone), the thickness of the adhesive layer can be reduced to about 0.1 times the average particle size of the conductive particles P. Become.
  • the amount of the organic solvent to be diluted is not particularly limited, but it is preferable to add 50 to 500 parts by mass with respect to 100 parts by mass of the adhesive component.
  • the drying temperature of the adhesive paste W is preferably, for example, 20 ° C to 80 ° C.
  • the transport speed of the support film 12 is preferably, for example, 30 mm / s to 160 mm / s.
  • the thickness of the adhesive paste W is preferably 5 ⁇ m to 10 ⁇ m, for example, when conductive particles P having an average particle size of 3 ⁇ m are used.
  • the adhesive paste W dries in a state where the conductive particles P are sufficiently separated from each other, so that the dispersion tends to be sufficient.
  • the transport speed of the support film 12 is 160 mm / s or less, the application of the magnetic field tends to end after drying, and the reaggregation of the conductive particles P can be suppressed.
  • the thickness of the adhesive paste W is 5 ⁇ m or more, it is possible to suppress the shortage of the gap of the coater 23 and the shortage of the number of conductive particles P in the first adhesive layer 13.
  • the thickness of the adhesive paste W is 10 ⁇ m or less, it is possible to suppress an excessive gap of the coater 23, and it is possible to suppress an excessive number of conductive particles P in the first adhesive layer 13.
  • the second adhesive layer 14 separately formed on the release film 15 is laminated on the first adhesive layer 13 (lamination step). ).
  • the circuit connection adhesive film 11 shown in FIG. 2 is obtained.
  • a hot roll laminator can be used for laminating the second adhesive layer 14.
  • the present invention is not limited to laminating, and an adhesive paste used as a material for the second adhesive layer 14 may be applied and dried on the first adhesive layer 13.
  • the thickness of the first adhesive layer 13 is 0.1 times or more and 1.0 times or less and 0.1 times or more and 0.7 times the average particle size of the conductive particles P.
  • It can be less than or equal to, or 0.6 times or more and less than 1.0 times. In this case, the flow of the conductive particles P during crimping is suppressed, and the capture efficiency of the conductive particles P between the first circuit electrode 6 and the second circuit electrode 8 can be improved. Therefore, the connection reliability between the first circuit member 2 and the second circuit member 3 can be ensured.
  • FIG. 10 is a perspective view showing an adhesive film accommodating set of one embodiment.
  • the adhesive film accommodating set 120 includes an adhesive film 11 for circuit connection, a reel 121 around which the adhesive film 11 is wound, and an accommodating member 122 accommodating the adhesive film 11 and the reel 121. And.
  • the adhesive film 11 is, for example, in the form of a tape.
  • the tape-shaped adhesive film 11 is produced, for example, by cutting a sheet-shaped raw fabric into a long length with a width suitable for the intended use.
  • the adhesive film 11 may have a support film 12 on the side of the first adhesive layer.
  • a base material such as the PET film described above can be used.
  • the reel 121 has a first side plate 124 having a winding core 123 around which the adhesive film 11 is wound, and a second side plate 125 arranged so as to face the first side plate 124 with the winding core 123 interposed therebetween. Be prepared.
  • the first side plate 124 is, for example, a disk made of plastic, and an opening having a circular cross section is provided in the central portion of the first side plate 124.
  • the winding core 123 of the first side plate 124 is a portion around which the adhesive film 11 is wound.
  • the winding core 123 is made of, for example, plastic, and has an annular shape having a thickness similar to the width of the adhesive film 11.
  • the winding core 123 is fixed to the inner surface of the first side plate 124 so as to surround the opening of the first side plate 124.
  • a shaft hole 126 is provided in the central portion of the reel 121, which is a portion into which a rotating shaft of a winding device or a feeding device (not shown) is inserted. When the rotating shaft is driven with the rotating shaft of the winding device or the feeding device inserted into the shaft hole 126, the reel 121 rotates without idling.
  • a desiccant container containing a desiccant may be fitted in the shaft hole 126.
  • the second side plate 125 is a disk made of, for example, plastic, and the central portion of the second side plate 125 has a circular cross section having the same diameter as the opening of the first side plate 124. The opening is provided.
  • the accommodating member 122 has a bag shape, for example, and accommodates the adhesive film 11 and the reel 121.
  • the accommodating member 122 has an insertion port 127 for accommodating (inserting) the adhesive film 11 and the reel 121 inside the accommodating member 122.
  • the accommodating member 122 has a visual recognition portion 128 that makes the inside of the accommodating member 122 visible from the outside.
  • the accommodating member 122 shown in FIG. 10 is configured such that the entire accommodating member 122 becomes a visual recognition portion 128.
  • the visual recognition unit 128 has transparency to visible light. For example, when the light transmittance in the visual recognition unit 128 is measured in the wavelength range of 450 to 750 nm, the average value of the light transmittance is 30% or more between the wavelengths of 450 to 750 nm, and the wavelength width is 50 nm. There is at least one region.
  • the light transmittance of the visual recognition unit 28 is obtained by preparing a sample obtained by cutting the visual recognition unit 128 to a predetermined size and measuring the light transmittance of the sample with an ultraviolet-visible spectrophotometer.
  • the accommodating member 122 has such a visual recognition portion 128, various information such as the product name, lot number, and expiration date affixed to the reel 121 inside the accommodating member 122 can be confirmed from the outside of the accommodating member 122. be able to. This can be expected to prevent mixing of different products and improve the efficiency of sorting work.
  • the transmittance of light having a wavelength of 365 nm in the visual recognition unit 128 is 10% or less. Since the transmittance of the light having a wavelength of 365 nm in the visual recognition unit 128 is 10% or less, the light incident from the outside to the inside of the accommodating member 122 when the photopolymerization initiator is used as the component (B) and the first Curing of the second curable composition due to the photopolymerization initiator remaining in the adhesive layer can be suppressed.
  • the transmittance of light having a wavelength of 365 nm in the visible portion 128 is preferably 10% or less, more preferably 5% or less, still more preferably. Is 1% or less, particularly preferably 0.1% or less.
  • the maximum value of the light transmittance in the wavelength region in which the above-mentioned photopolymerization initiator (component (B)) can generate radicals, cations or anions in the visual recognition unit 128 is preferable. It is 10% or less, more preferably 5% or less, still more preferably 1% or less, and particularly preferably 0.1% or less.
  • the maximum value of the light transmittance in the viewing unit 128 at a wavelength of 254 to 405 nm is preferably 10% or less, more preferably 5% or less, still more preferably 1% or less, and particularly preferably 0.1%. It is as follows.
  • the visual recognition portion 128 (accommodating member 122) is formed of, for example, a sheet having a thickness of 10 to 5000 ⁇ m.
  • the sheet is made of a material having a transmittance of light having a wavelength of 365 nm in the visible portion 128 of 10% or less.
  • a material may consist of one type of component or may consist of a plurality of types of components. Examples of the material include low-density polyethylene, linear low-density polyethylene, polycarbonate, polyester, acrylic resin, polyamide, glass and the like. These materials may contain UV absorbers.
  • the visual recognition unit 128 may have a laminated structure formed by laminating a plurality of layers having different light transmission properties. In this case, each layer constituting the visual recognition unit 128 may be made of the above-mentioned material.
  • the insertion port 127 may be sealed by, for example, being closed by a sealing machine or the like in order to prevent air from entering from the outside during accommodation. In this case, it is preferable to suck and remove the air in the accommodating member 122 before closing the insertion port 127. It can be expected that the humidity inside the accommodating member 122 will be reduced from the initial stage of accommodating and that air will be prevented from entering from the outside. Further, when the inner surface of the accommodating member 122 and the reel 121 are in close contact with each other, the inner surface of the accommodating member 122 and the surface of the reel 121 rub against each other due to vibration during transportation to generate foreign matter, and the side plate 124 of the reel 121 , 125 can be prevented from being scratched on the outer surface.
  • the accommodating member is configured so that the entire accommodating member serves as a visible portion, but in another embodiment, the accommodating member has a visible portion as a part of the accommodating member. May be good.
  • the accommodating member may have a rectangular visible portion substantially in the center of the side surface of the accommodating member.
  • the portion of the accommodating member other than the visible portion may be black, for example, so as not to transmit ultraviolet light and visible light.
  • the shape of the accommodating member is bag-shaped, but the accommodating member may be, for example, box-shaped.
  • the accommodating member preferably has a notch for opening. In this case, the opening work at the time of use becomes easy.
  • ⁇ Preparation method of polyester urethane resin 48 parts by mass of isophthalic acid and 37 parts by mass of neopentyl glycol were put into a heated stainless steel autoclave equipped with a stirrer, a thermometer, a condenser, a vacuum generator and a nitrogen gas introduction tube, and tetrabutoxy as a catalyst. 0.02 parts by mass of titanate was added. Then, the temperature was raised to 220 ° C. under a nitrogen stream, and the mixture was stirred as it was for 8 hours. Then, the pressure was reduced to atmospheric pressure (760 mmHg), the mixture was cooled to room temperature, the white precipitate was taken out, washed with water, and vacuum dried to obtain a polyester polyol.
  • the polyester polyol obtained by the above-mentioned reaction between the dicarboxylic acid and the diol is sufficiently dried, then dissolved in MEK, and placed in a four-necked flask equipped with a stirrer, a dropping funnel, a reflux cooler and a nitrogen gas introduction tube. did. Further, dibutyltin laurate was added as a catalyst in an amount of 0.05 parts by mass with respect to 100 parts by mass of the polyester polyol, and 4,4′-diphenylmethane diisocyanate dissolved in MEK was 50 parts by mass with respect to 100 parts by mass of the polyester polyol.
  • the desired polyester urethane resin was obtained by adding the above amount with a dropping funnel and stirring at 80 ° C. for 4 hours.
  • polyurethane acrylate (UA1) was obtained.
  • the weight average molecular weight of the polyurethane acrylate (UA1) was 15,000.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve according to the following conditions.
  • GPC gel permeation chromatography
  • ⁇ Making conductive particles> A layer made of nickel was formed on the surface of the polystyrene particles so that the thickness of the layer was 0.2 ⁇ m. In this way, conductive particles having an average particle size of 4 ⁇ m, a maximum particle size of 4.5 ⁇ m, and a specific gravity of 2.5 were obtained.
  • A1 Dicyclopentadiene type diacrylate (trade name: DCP-A, manufactured by Toagosei Co., Ltd.)
  • A2 Polyurethane acrylate synthesized as described above (UA1)
  • A3 2-methacryloyloxyethyl acid phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.)
  • B1 B1: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (trade name: Irgacure (registered trademark) OXE01, manufactured by BASF)
  • C1 Benzoyl peroxide (trade name: Niper BMT-K40, manufactured by NOF CORPORATION) (Conductive particles)
  • D1 Conductive particles (thermoplastic resin) prepared as described above
  • E1 Polyester
  • thermosetting composition varnish (varnish composition)> As polymerizable compounds a1 to a3, thermoplastic resin e1, coupling agent f1, filler g1 and solvent h1, the polymerizable compounds A1 to A3, the thermoplastic resin E1, the coupling agent F1 and the filler in the photocurable composition. Using the same G1 and solvent H1, these components and the thermal polymerization initiator shown below were mixed in the blending amounts (parts by mass) shown in Table 2 to prepare a varnish for the thermosetting composition 1. The content (% by volume) of the filler shown in Table 2 is a content based on the total volume of the thermosetting composition. (Thermal polymerization initiator) c1: Benzoyl peroxide (trade name: Niper BMT-K40, manufactured by NOF CORPORATION)
  • Example 1 [Preparation of the first adhesive film]
  • the varnish of the photocurable composition 1 was applied onto a PET film having a thickness of 50 ⁇ m using a coating device.
  • hot air drying was performed at 70 ° C. for 3 minutes, and a magnetic field was applied at the same time to form a layer made of the photocurable composition 1 having a thickness (thickness after drying) of 4 ⁇ m on the PET film.
  • the thickness was measured using a contact type thickness gauge. When a contact type thickness gauge is used, the size of the conductive particles is reflected, and the thickness of the region where the conductive particles are present is measured.
  • the thickness of the first adhesive layer located at the separated portion of the adjacent conductive particles is obtained by the method described later.
  • the layer made of the photocurable composition 1 was irradiated with light using a metal halide lamp so that the integrated light amount was 1500 mJ / cm 2 , and the polymerizable compound was polymerized.
  • the photocurable composition 1 was cured to form a first adhesive layer.
  • a first adhesive film having a first adhesive layer having a thickness of 4 ⁇ m (thickness of the region where the conductive particles are present) on the PET film was obtained.
  • the conductive particle density at this time was about 7000 pcs / mm 2 .
  • the monodispersity of the conductive particles (the ratio at which the conductive particles exist in a state of being separated from other adjacent conductive particles (monodisperse state)) was evaluated.
  • the monodispersity rate was 70% or more.
  • the monodisperse rate, the monodispersion ratio (%) (2500 ⁇ m 2 in conductive particle number monodisperse / 2500 [mu] m conductive particle count in 2) ⁇ 100, was calculated using.
  • the conductive particles were actually measured using a metallurgical microscope at a magnification of 200 times.
  • thermosetting composition 1 The varnish of the thermosetting composition 1 was applied onto a PET film having a thickness of 50 ⁇ m using a coating device. Next, hot air drying was performed at 70 ° C. for 3 minutes to form a second adhesive layer (layer composed of the thermosetting composition 1) having a thickness of 8 ⁇ m on the PET film. By the above operation, a second adhesive film having a second adhesive layer on the PET film was obtained.
  • An adhesive film for circuit connection is sandwiched between two sheets of glass (thickness: about 1 mm), and 100 g of bisphenol A type epoxy resin (trade name: JER811, manufactured by Mitsubishi Chemical Corporation) and a curing agent (trade name: Epomount curing agent) , Made by Refine Tech Co., Ltd.)
  • a resin composition consisting of 10 g the cross section is polished using a polishing machine, and a scanning electron microscope (SEM, trade name: SE-8020, manufactured by Hitachi High-Tech Science Co., Ltd.)
  • SEM scanning electron microscope
  • the width of the glass substrate with a glass substrate (manufactured by Geomatec) is heated and pressurized at 170 ° C. and 6 MPa for 4 seconds using a heat crimping device (heating method: constant heat type, manufactured by Taiyo Kikai Co., Ltd.).
  • a circuit connection structure (connection structure) was produced by connecting over 1 mm. At the time of connection, the circuit connection adhesive film was first attached to the COF substrate from the second adhesive layer side, and after the separator was peeled off, the separator was opposed to the glass substrate to heat and pressurize.
  • connection resistance value between the opposing electrodes immediately after the connection was measured with a multimeter.
  • the connection resistance value was determined as the average value of 16 resistance points between the opposing electrodes.
  • the results are shown in Table 3.
  • the particle dispersibility after mounting was observed using a microscope. The one in which the state before mounting was maintained was evaluated as 1, the one in which the state before mounting was not maintained as 3, and the intermediate was evaluated as 2. Levels 1 and 2 are practically acceptable levels.
  • Example 2 An adhesive film for circuit connection and a circuit connection structure were produced in the same manner as in Example 1 except that the thickness of the first adhesive layer was changed to 1.5 ⁇ m and 3.0 ⁇ m.
  • the prepared circuit connection structure was evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • the monodispersity of the conductive particles in the first adhesive layer was 70% or more, respectively.

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JP7124948B1 (ja) 2021-12-15 2022-08-24 株式会社リコー 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク組成物、インクジェット用インク組成物、組成物収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、硬化物、加飾体、積層体、フレキシブルデバイス用部材、及びフレキシブルデバイス
JP2023088774A (ja) * 2021-12-15 2023-06-27 株式会社リコー 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク組成物、インクジェット用インク組成物、組成物収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、硬化物、加飾体、積層体、フレキシブルデバイス用部材、及びフレキシブルデバイス
JP2023088831A (ja) * 2021-12-15 2023-06-27 株式会社リコー 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク組成物、インクジェット用インク組成物、組成物収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、硬化物、加飾体、積層体、フレキシブルデバイス用部材、及びフレキシブルデバイス
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WO2024034464A1 (ja) * 2022-08-10 2024-02-15 株式会社レゾナック 回路接続用接着剤フィルム、並びに回路接続構造体及びその製造方法

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