WO2020184585A1 - 回路接続用接着剤フィルム及びその製造方法、回路接続構造体の製造方法、並びに、接着剤フィルム収容セット - Google Patents
回路接続用接着剤フィルム及びその製造方法、回路接続構造体の製造方法、並びに、接着剤フィルム収容セット Download PDFInfo
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- WO2020184585A1 WO2020184585A1 PCT/JP2020/010388 JP2020010388W WO2020184585A1 WO 2020184585 A1 WO2020184585 A1 WO 2020184585A1 JP 2020010388 W JP2020010388 W JP 2020010388W WO 2020184585 A1 WO2020184585 A1 WO 2020184585A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C09J171/12—Polyphenylene oxides
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistors
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits by conductive adhesives
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/36—Assembling printed circuits with other printed circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/36—Assembling printed circuits with other printed circuits
- H05K3/361—Assembling flexible printed circuits with other printed circuits
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
Definitions
- the present invention relates to an adhesive film for circuit connection and a method for manufacturing the same, 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.
- Patent Document 1 proposes a method in which conductive particles are unevenly distributed on one side of an anisotropic conductive adhesive sheet to separate the conductive particles from each other.
- connection resistance after placing may increase.
- the present invention suppresses the flow of conductive particles in the adhesive film at the time of circuit connection, and also suppresses an increase in connection resistance immediately after the circuit connection structure is connected and after being placed in a high temperature and high humidity environment.
- the purpose is.
- One aspect of the present invention is a circuit connection adhesive film comprising a first adhesive layer containing conductive particles and a second adhesive layer laminated on the first adhesive layer.
- the shortest distance from the surface of the adhesive film on the side of the first adhesive layer to the surface of the conductive particles is more than 0 ⁇ m and 1 ⁇ m or less, and the ratio of the thickness of the first adhesive layer to the average particle size of the conductive particles. Is 10% or more and 80% or less, and the ratio of the thickness of the second adhesive layer to the total thickness of the first adhesive layer and the second adhesive layer is less than 96%. It is an adhesive film.
- this circuit connection adhesive film the flow of conductive particles when connecting circuit members is suppressed, so that the conductive particles are suitably trapped between the electrodes facing each other, and the risk of short circuit is reduced.
- this circuit connection adhesive film it is possible to suppress an increase in connection resistance in the circuit connection structure immediately after connection and after being placed in a high temperature and high humidity environment (for example, 85 ° C., 85% RH).
- the first adhesive layer may consist of a cured product of the first curable composition, the first curable composition containing a radically polymerizable compound having a radically polymerizable group. You can.
- 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 production method includes a preparation step of preparing a first adhesive layer, and a laminating step of laminating a second adhesive layer made of a second curable composition on the first adhesive layer.
- the first curable composition is cured by irradiating or heating the layer composed of the first curable composition containing conductive particles with light, and the first adhesive layer is prepared.
- the shortest distance from the surface of the adhesive film on the first adhesive layer side to the surface of the conductive particles is more than 0 ⁇ m and 1 ⁇ m or less, and the first adhesive with respect to the average particle size of the conductive particles.
- the ratio of the layer thickness is 10% or more and 80% or less, and the ratio of the thickness of the second adhesive layer to the total thickness of the first adhesive layer and the second adhesive layer is less than 96%.
- the first curable composition may further contain a radically polymerizable compound having a radically polymerizable group.
- the second curable composition may contain a radically polymerizable compound having a radically polymerizable group.
- the circuit connection adhesive film is interposed between the first circuit member having the first electrode and the second circuit member having the second electrode.
- Another aspect of the present invention includes the above-mentioned adhesive film for circuit connection and an accommodating member for accommodating the adhesive film, and the accommodating member is a visual recognition portion that makes the inside of the accommodating member visible from the outside.
- This is an adhesive film accommodating set having a light transmittance of 10% or less at a wavelength of 365 nm in the visible portion.
- the environment in which the adhesive film for circuit connection is used is called a clean room, in which the temperature, humidity and cleanliness of the room are controlled at a certain level.
- a storage member such as a packing bag so that it will not be directly exposed to the outside air and cause quality deterioration due to dust and humidity.
- this accommodating member is made of a transparent material so that various information such as the product name, lot number, and expiration date attached to the internal adhesive film can be confirmed from outside the accommodating member. A part is provided.
- the first adhesive layer is composed of a cured product of a photocurable composition
- the second adhesive layer is a photocurable composition
- the second adhesive layer may be cured during storage and transportation of the adhesive film, and the above-mentioned problems may occur. It was revealed. Therefore, the present inventors further speculate that the polymerization of the polymerizable compound in the second adhesive layer is proceeding by the radicals derived from the photopolymerization initiator remaining in the first adhesive layer. As a result of examination, by using an adhesive film accommodating set provided with the specific accommodating member, it is possible to suppress the curing of the second adhesive layer during storage or transportation, and to suppress the occurrence of the above-mentioned defects. I found out what I could do.
- the adhesive film accommodating set on one side of the present invention when a compound capable of reacting with the photopolymerization initiator in the first adhesive layer is used as the polymerizable compound in the second adhesive layer. It is possible to suppress the curing of the second adhesive layer during storage or transportation of the adhesive film, and it is possible to suppress the occurrence of problems such as a decrease in the effect of reducing the connection resistance of the adhesive film.
- the flow of conductive particles in the adhesive film at the time of circuit connection is suppressed, and the increase in connection resistance is suppressed immediately after the circuit connection structure is connected and after being placed in a high temperature and high humidity environment. be able to.
- FIG. 1 is a schematic cross-sectional view showing an adhesive film for circuit connection according to an embodiment.
- FIG. 2 is a schematic cross-sectional view showing a main part of the circuit connection adhesive film shown in FIG.
- FIG. 3 is a schematic cross-sectional view showing a circuit connection structure of one embodiment.
- FIG. 4 is a schematic cross-sectional view showing a method of manufacturing the circuit connection structure of one embodiment.
- FIG. 5 is a perspective view showing an adhesive film accommodating set of one embodiment.
- (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 1 (hereinafter, also simply referred to as “adhesive film 1”) is laminated on the first adhesive layer 2 and the first adhesive layer 2.
- a second adhesive layer 3 is provided.
- the conductive particles 4 are dispersed in the first adhesive layer 2. That is, the first adhesive layer 2 contains the conductive particles 4. Therefore, the adhesive film 1 can be an anisotropically conductive adhesive film having anisotropic conductivity.
- the adhesive film 1 is interposed between the first circuit member having the first electrode and the second circuit member having the second electrode, and holds the first circuit member and the second circuit member. It is thermocompression bonded and used to electrically connect the first electrode and the second electrode to each other.
- the first adhesive layer 2 is made of, for example, a cured product of the first curable composition.
- the first curable composition may be a photocurable composition, may be a thermosetting composition, and may be a photo / thermosetting composition (a composition having both photocurability and thermosetting). ) May be.
- 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 4 (hereinafter, also referred to as “component (C)”).
- 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). When the first curable composition is a thermosetting composition, the first curable composition contains a thermopolymerization 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 polymerize the first curable composition. It is obtained by curing. That is, the first adhesive layer 2 may be composed of the conductive particles 4 and the first adhesive component 5 obtained by curing components other than the conductive particles 4 of the first curable composition.
- the first adhesive layer 2 may be a cured product obtained by completely curing the first curable composition, or may be a cured product obtained by partially curing the first curable composition. Good. That is, when the first curable composition contains the component (A) and the component (B), the first adhesive component 5 contains the unreacted component (A) and the component (B). It may or may not be contained.
- 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 group is preferably a radically polymerizable group that reacts with radicals from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment. That is, the component (A) is preferably a radically polymerizable compound having a radically polymerizable group.
- 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 of further suppressing an increase in connection resistance in a high temperature and high humidity environment after polymerization, and from the viewpoint of suppressing curing shrinkage during polymerization. It may be 10 or less.
- the component (A) in order to balance the crosslink density and the curing shrinkage, in addition to the polymerizable compound having the number of polymerizable groups within the above range, the component (A) further contains a polymerizable compound having the number of polymerizable groups outside the above range. It may be included.
- 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) preferably contains one or more (meth) acrylate compounds from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- the component (A) preferably contains a (meth) acrylate compound having a high Tg skeleton such as a dicyclopentadiene skeleton from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- the component (A) preferably has a vinyl group or an allyl group at the end or side chain of a thermoplastic resin such as an acrylic resin, a phenoxy resin, or a polyurethane resin from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- a thermoplastic resin such as an acrylic resin, a phenoxy resin, or a polyurethane resin from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- a thermoplastic resin such as an acrylic resin, a phenoxy resin, or a polyurethane resin from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- a thermoplastic resin such as an acrylic resin, a phenoxy resin, or a polyurethane resin from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- 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.
- 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) may be 5% by mass or more based on the total mass of the first curable composition from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment, and may be 10% by mass. It may be% or more, it may be 20% by mass or more, and it may be 30% 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, 60% by mass or less, 50% by mass or less, and 40% 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 preferably a radical polymerization initiator (photoradical polymerization initiator or thermal radical polymerization initiator) from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- the component (B) one kind of compound may be used alone, or a plurality of kinds of compounds may be used in combination.
- 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.
- Photoradical polymerization initiators include oxime ester structure, bisimidazole structure, aclydin structure, ⁇ -aminoalkylphenone structure, aminobenzophenone structure, N-phenylglycine structure, acylphosphine oxide structure, benzyldimethylketal structure, ⁇ -hydroxy. Examples thereof include compounds having a structure such as an alkylphenone structure.
- the photoradical polymerization initiator preferably has at least one structure selected from the group consisting of an oxime ester structure, an ⁇ -aminoalkylphenone structure and an acylphosphine oxide structure from the viewpoint of being more excellent in reducing the connection resistance.
- 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).
- 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 further excellent effect of reducing connection resistance. It may be 0.5% by mass or more, 1% by mass or more, and 2% by mass or more. The content of the component (B) is 15% by mass or less based on the total mass of the first curable composition from the viewpoint of improving the storage stability and further excellent in the effect of reducing the 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), from the viewpoint of facilitating the production of a circuit connection adhesive film. It is more preferable to contain a photopolymerization initiator, and further preferably to contain a photopolymerization initiator and a thermal polymerization initiator.
- 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 above-mentioned various conductive particles 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, 20 ⁇ m or less, 10 ⁇ m or less, and 5 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity. It may be.
- 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, 20 ⁇ m or less, 10 ⁇ m or less, and 5 ⁇ m or less from the viewpoint of excellent dispersibility and conductivity. It may be.
- 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) first in the adhesive layer 2, from the viewpoint of improving the insulating property between adjacent electrodes may be at 100000pcs / mm 2 or less, may be at 50000pcs / mm 2 or less, It may be 10000 pcs / mm 2 or less.
- the content of the component (C) may be 0.1% by volume or more and 1% by volume or more based on the total volume of the first adhesive layer from the viewpoint of further improving the conductivity. 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, or 20% by volume based on the total volume of the first adhesive layer from the viewpoint of easily suppressing a short circuit. It may be: 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 content of the component (C) may be 5% by mass or more, or 10% by mass or more, based on the total mass of the first adhesive layer, from the viewpoint of further improving the conductivity. , 15% by mass or more, and may be 20% by mass or more.
- the content of the component (C) may be 60% by mass or less, 50% by mass or less, and 40% by mass based on the total mass of the first adhesive layer from the viewpoint of easily suppressing a short circuit. It may be less than or equal to 30% by mass or less.
- the content of the component (C) in the first curable composition (based on the total mass 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 2.
- thermoplastic resin examples include phenoxy resin, polyester resin, polyamide resin, polyurethane resin, polyester urethane resin, acrylic rubber and the like.
- the first curable composition contains a thermoplastic resin
- the first adhesive layer can be easily formed.
- the first curable composition contains a thermoplastic resin
- the stress of the first adhesive layer generated at the time of curing of the first curable composition can be relieved.
- the thermoplastic resin may have a functional group such as a hydroxyl group, and in this case, 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, 10% by mass or more, or 20% by mass or more based on the total mass of the first curable composition. It may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, and 40% by mass or less.
- 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, 0.5% by mass or more, and 20% by mass or less based on the total mass of the first curable composition. It may be 10% by mass or less, 5% by mass or less, and 2% by mass or less.
- 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 4.
- the content of the filler may be, for example, 0.1% by volume or more and 50% by volume or less based on the total volume of the first curable composition.
- the content of the filler may be, for example, 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more based on the total mass of the first curable composition. It may be 50% by mass or less, 30% by mass or less, 10% by mass or less, and 5% by mass or less.
- 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% by mass or more and 10% by mass or less based on the total mass of the first curable composition. These additives may be contained in the first adhesive layer 2.
- the first curable composition may contain a thermosetting resin in place of 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 thermosetting group.
- 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.
- the thermosetting group may be, for example, an epoxy group, an oxetane group, an isocyanate group, or the like from the viewpoint of further suppressing an increase in connection resistance in a high temperature and high humidity environment.
- 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 2 may contain components derived from the first curable composition such as unreacted components (A) and (B).
- the unreacted component (B) remains in the first adhesive layer 2 during storage and transportation.
- a part of the second curable composition in the second adhesive layer 3 is cured, and peeling easily occurs 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 effect of reducing the connection resistance of the film 1 will occur.
- the content of the unreacted component (B) in the first adhesive layer 2 is 15% by mass or less based on the total mass of the first adhesive layer. It may be 10% by mass or less, and may be 5% by mass or less. The content of the unreacted component (B) in the first adhesive layer 2 may be 0.1% by mass or more based on the total mass of the first adhesive layer.
- the second adhesive layer 3 is composed of, for example, a second adhesive component 6 which is 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 photo-thermosetting composition (a composition having both photo-curing property and thermosetting property).
- the second curable composition constituting the second adhesive layer 3 is an uncured curable composition that can flow when connected to a circuit.
- 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) is a radically polymerizable compound having a radically polymerizable group that reacts with radicals from the viewpoint of facilitating connection at low temperature for a short time, further improving the effect of reducing connection resistance, and improving connection reliability. Is preferable.
- 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) may be 10% by mass or more based on the total mass of the second curable composition from the viewpoint that the crosslink density required for further reducing the connection resistance can be easily obtained. It may be 20% by mass or more, 30% by mass or more, and 40% 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 0% by mass or less, 70% by mass or less, 60% by mass or less, and 50% 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 second curable composition preferably contains at least one of a photopolymerization initiator and a thermal polymerization initiator as the component (b), and is more preferably thermally polymerized from the viewpoint of further facilitating circuit connection. It contains an initiator, more preferably only a thermal polymerization initiator.
- 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, 1% by mass or more, and 2% 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 5% by mass or less.
- 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 2.
- 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 4 in the second adhesive layer 3 may be, for example, 1% by mass or less, or 0% by mass, based on the total mass of the second adhesive layer.
- the second adhesive layer 3 preferably does not contain the conductive particles 4.
- the adhesive film 1 is composed of a region (existing region) R1 in which the conductive particles 4 exist and a region (absent region) R2 in which the conductive particles 4 do not exist when viewed from the stacking direction.
- the adhesive film 1 contains the first adhesive component 5, the conductive particles 4, the first adhesive component 5, and the second adhesive component 6 on the first adhesive layer 2 side. It is provided in this order in the stacking direction. That is, the first adhesive component 5 is present between the surface 2a of the first adhesive layer 2 opposite to the second adhesive layer 3 and the conductive particles 4, and the conductive particles. The first adhesive component 5 is also present on the surface of No. 4 on the side of the second adhesive layer 3 so as to cover the surface.
- the shortest distance D from the surface 2a on the first adhesive layer 2 side of the adhesive film 1 to the surface of the conductive particles 4 suppresses an increase in connection resistance in a high temperature and high humidity environment, and the conductive particles at the time of circuit connection From the viewpoint of suppressing the flow, it is more than 0 ⁇ m and 1 ⁇ m or less. From the same viewpoint, the shortest distance D may be 0.1 ⁇ m or more, 0.2 ⁇ m or more, or 0.8 ⁇ m or less.
- the surface 2a of the first adhesive layer 2 opposite to the second adhesive layer 3 constitutes one surface 2a of the adhesive film 1 (that is, the first adhesion).
- the shortest distance D is the side opposite to the second adhesive layer 3 of the first adhesive layer 2. It can also be said that it is the shortest distance from the surface 2a to the surface of the conductive particles 4.
- the shortest distance d11 from the interface S of the first adhesive layer 2 and the second adhesive layer 3 to the surface of the conductive particles 4 may be, for example, 0.1 ⁇ m or more, 3.0 ⁇ m or less, 2.0 ⁇ m or less. It may be less than or equal to 1.0 ⁇ m or less.
- the first adhesive component may not be present on the surface of the conductive particles 4 on the side of the second adhesive layer 3. That is, it can be said that the shortest distance d11 may be 0 ⁇ m or more.
- the shortest distance d21 from the interface S of the first adhesive layer 2 and the second adhesive layer 3 to the surface 3a of the second adhesive layer 3 opposite to the first adhesive layer 2 in the existing region R1. May be, for example, 0.5 ⁇ m or more, 1.0 ⁇ m or more, 2.0 ⁇ m or more, 3.0 ⁇ m or more, 5.0 ⁇ m or more, or 10 ⁇ m or more, and may be 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or It may be 10 ⁇ m or less.
- the adhesive film 1 includes a first adhesive component 5 and a second adhesive component 6 in the absent region R2 in this order from the first adhesive layer 2 side in the stacking direction.
- the first adhesive component 5 exists so as to cover the surface of the conductive particles 4 (including the surface on the side of the second adhesive layer 3). Therefore, the interface S of the first adhesive layer 2 and the second adhesive layer 3 is the conductive particles in the non-existent region R2 in the vicinity of the conductive particles 4 (near the boundary between the existing region R1 and the non-existent region R2).
- the surface 2a on the opposite side of the surface 2a and the surface 3a on the opposite side of the first adhesive layer 2 of the second adhesive layer 3 are substantially parallel to each other.
- the thickness of the first adhesive layer 2 is the thickest in the vicinity of the conductive particles 4, and becomes thinner as the distance from the conductive particles 4 increases.
- the thickness of the second adhesive layer 3 is the thinnest in the vicinity of the conductive particles 4, and becomes thicker as the distance from the conductive particles 4 increases.
- the thickness of the first adhesive layer and the thickness of the second adhesive layer are the thickness of the first adhesive layer and the thickness of the second adhesive layer in the absent region R2 in which the conductive particles 4 do not exist. Each is defined as the thickness of the adhesive layer. Further, a preferable range of the thickness of the first adhesive layer and the thickness of the second adhesive layer will be described below, but the following describes the first adhesive layer at an arbitrary position in the absent region R2.
- the thickness d12 in the vicinity of the conductive particles 4 and the thickness d13 at a position away from it is preferably within the range shown below.
- the thickness of the first adhesive layer 2 is smaller than the average particle size of the conductive particles 4.
- the ratio of the thickness of the first adhesive layer 2 to the average particle size of the conductive particles 4 is when the circuit is connected. It is 10% or more from the viewpoint of suppressing the flow of the conductive particles 4 of the above, and 80% or less from the viewpoint of suppressing an increase in the connection resistance.
- the ratio is preferably 15% or more, more preferably 20% or more, from the viewpoint of further suppressing the flow of the conductive particles 4 at the time of circuit connection. From the viewpoint of further suppressing the increase in connection resistance, the ratio is preferably 70% or less, more preferably 60% or less, still more preferably 55% or less, and particularly preferably 50% or less.
- the thickness of the second adhesive layer 3 is a predetermined ratio to the total thickness of the first adhesive layer 2 and the second adhesive layer 3. Specifically, the ratio of the thickness of the second adhesive layer 3 to the total thickness of the first adhesive layer 2 and the second adhesive layer 3 (thickness of the second adhesive layer 3 / first The total thickness of the adhesive layer 2 and the second adhesive layer 3 of 1) is less than 96% from the viewpoint of suppressing the flow of the conductive particles 4 at the time of circuit connection.
- the ratio is preferably 94% or less, more preferably 93% or less, further preferably 88% or less, and particularly preferably 86% or less, from the viewpoint of further suppressing the flow of the conductive particles 4 at the time of circuit connection.
- the ratio may be, for example, 75% or more, 78% or more, or 80% or more.
- the thickness of the first adhesive layer 2 may be, for example, 0.3 ⁇ m or more, 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less, although it depends on the size of the conductive particles.
- the thickness of the second adhesive layer 3 may be 5 ⁇ m or more, and may be 200 ⁇ m, from the viewpoint that the space between the electrodes can be sufficiently filled to seal the electrodes and better reliability can be obtained. Hereinafter, it may be 100 ⁇ m or less, 50 ⁇ m or less, or 20 ⁇ m or less.
- the total thickness of the first adhesive layer 2 and the second adhesive layer 3 may be, for example, 5 ⁇ m or more, 6 ⁇ m or more, or 7 ⁇ m or more, 200 ⁇ m or less, 100 ⁇ m. Hereinafter, it may be 50 ⁇ m or less, or 20 ⁇ m or less.
- circuit connection adhesive film of the present embodiment has been described above, the present invention is not limited to the above embodiment.
- the adhesive film for circuit connection may be composed of two layers, a first adhesive layer and a second adhesive layer, other than the first adhesive layer and the second adhesive layer. It may be composed of three or more layers including a layer (for example, a third adhesive layer).
- the third adhesive layer may be a layer having the same composition as that described above for the first adhesive layer or the second adhesive layer, and may be the first adhesive layer or the second adhesive layer. It may be a layer having the same thickness as the above-mentioned thickness.
- the circuit connection adhesive film may further include, for example, a third adhesive layer on the opposite surface of the second adhesive layer in the first adhesive layer.
- the circuit connection adhesive film is formed by, for example, laminating a second adhesive layer, a first adhesive layer, and a third adhesive layer in this order.
- the shortest distance from the surface of the adhesive film on the side of the first adhesive layer (in this case, the surface of the third adhesive layer) to the surface of the conductive particles is more than 0 ⁇ m and 1 ⁇ m or less.
- the third adhesive layer is made of, for example, a second curable composition (for example, a thermosetting composition) like the second adhesive layer.
- the circuit connection adhesive film of the above embodiment is an anisotropically conductive adhesive film having anisotropic conductivity, but the circuit connection adhesive film is a conductive adhesive having no anisotropic conductivity. It may be a film.
- the method for manufacturing the circuit connection adhesive film 1 of the present embodiment is, for example, a preparation step for preparing the first adhesive layer 2 described above (first preparation step) and a method for producing the adhesive film 1 for circuit connection on the first adhesive layer 2. It includes a laminating step of laminating the second adhesive layer 3 described above.
- the method for manufacturing the circuit connection adhesive film 1 may further include a preparation step (second preparation step) for preparing the second adhesive layer 3.
- the first adhesive layer 2 is formed on the base material.
- 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 made of the first curable composition is irradiated with light or heated to cure the first curable composition and form the first adhesive layer 2 on the substrate. (Curing step).
- 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 base material is not particularly limited as long as it has heat resistance that can withstand the heating conditions when the organic solvent is volatilized when the first curable composition is cured by light
- the first curable composition is not particularly limited.
- 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 base material examples include stretched polypropylene (OPP), polyethylene terephthalate (PET), polyethylene naphthalate, polyethylene isophthalate, polyvinylidene terephthalate, polyolefin, polyacetate, polycarbonate, polyvinylidene sulfide, polyamide, polyimide, cellulose, ethylene / acetic acid.
- a base material for example, a film made of a vinyl copolymer, polyvinyl chloride, polyvinylidene chloride, synthetic rubber, liquid crystal polymer or the like can be used.
- the heating conditions for volatilizing the organic solvent from the varnish composition applied to the base material 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, 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 heating conditions may be, for example, 30 ° C. or higher and 300 ° C. or lower for 0.1 minutes or longer and 5000 minutes or shorter, and 50 ° C. or higher and 150 ° C. or lower for 0.1 minutes or longer and 3000 minutes or shorter.
- the curing step is not performed (light irradiation and heating are not performed). Formes a second adhesive layer 3 on the base material in the same manner as in the first preparation step.
- the first adhesive layer 2 prepared in the first preparation step and the second adhesive layer 3 prepared in the second preparation step are bonded to each other to form a first.
- the second adhesive layer 3 may be laminated on the adhesive layer 2.
- the component (a) and the component (b), and other components added as needed are used on the first adhesive layer 2 prepared in the first preparing step.
- the second adhesive layer 3 may be laminated on the first adhesive layer 2 by applying the varnish composition to be obtained and volatilizing the organic solvent.
- Examples of the method of bonding the first adhesive layer 2 and the second adhesive layer 3 include a method such as heat pressing, roll laminating, and vacuum laminating. Lamination may be performed, for example, under heating conditions of 0 to 80 ° C.
- Circuit connection structure and its manufacturing method> a circuit connection structure using the above-mentioned circuit connection adhesive film 1 as a circuit connection material and a method for manufacturing the same will be described.
- FIG. 3 is a schematic cross-sectional view showing a circuit connection structure of one embodiment.
- the circuit connection structure 10 includes a first circuit member 13 having a first electrode 12 formed on the main surface 11a of the first circuit board 11 and the first circuit board 11. , A second circuit member 16 having a second electrode 15 formed on the main surface 14a of the second circuit board 14 and the second circuit board 14, and the first circuit member 13 and the second circuit member.
- a circuit connecting portion 17 which is arranged between 16 and electrically connects the first electrode 12 and the second electrode 15 to each other is provided.
- the first circuit member 13 and the second circuit member 16 may be the same or different from each other.
- the first circuit member 13 and the second circuit member 16 may be a glass substrate or a plastic substrate on which electrodes are formed, a printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor silicon IC chip, or the like.
- the first circuit board 11 and the second circuit board 14 may be formed of an inorganic substance such as semiconductor, glass, or ceramic, an organic substance such as polyimide or polycarbonate, or a composite such as glass / epoxy.
- the first electrode 12 and the second electrode 15 are gold, silver, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, aluminum, molybdenum, titanium, indium tin oxide (ITO), and indium zinc oxide. It may be made of a substance (IZO), indium gallium zinc oxide (IGZO), or the like.
- the first electrode 12 and the second electrode 15 may be circuit electrodes or bump electrodes. At least one of the first electrode 12 and the second electrode 15 may be a bump electrode. In FIG. 3, the second electrode 15 is a bump electrode.
- the circuit connection portion 17 is formed of the adhesive film 1 described above.
- the circuit connection portion 17 is made of, for example, a cured product of the adhesive film 1.
- the circuit connection portion 17 has, for example, a first cured product 18, a second cured product 19, and conductive particles 4.
- the first cured product 18 is located on the side of the first circuit member 13 in the direction in which the first circuit member 13 and the second circuit member 16 face each other (hereinafter, "opposing direction").
- the first cured product 18 is a cured product of the first adhesive component 5 (components (A), (B) and the like other than the conductive particles 4) in the above-mentioned first curable composition.
- the second cured product 19 is located on the side of the second circuit member 16 in the opposite direction.
- the second cured product 19 is a cured product of the above-mentioned second curable composition (second adhesive component 6) containing the component (a), the component (b), and the like.
- the conductive particles 4 are interposed between at least the first electrode 12 and the second electrode 15 to electrically connect the first electrode 12 and the second electrode 15 to each other.
- the circuit connection portion does not have to have two cured products in separate regions as in the first cured product 18 and the second cured product 19 described above, for example, the first adhesive component described above. It has a cured product in which a cured product of 5 (a component other than the conductive particles 4 in the first curable composition) and a cured product of the second adhesive component 6 (a second curable composition) are mixed. You may.
- FIG. 4 is a schematic cross-sectional view showing a method of manufacturing the circuit connection structure 10.
- a method of manufacturing the circuit connection structure 10 is, for example, between a first circuit member 13 having a first electrode 12 and a second circuit member 16 having a second electrode 15.
- the above-mentioned adhesive film 1 is interposed, the first circuit member 13 and the second circuit member 16 are thermocompression bonded, and the first electrode 12 and the second electrode 15 are electrically connected to each other.
- a first circuit including a first electrode 12 formed on a first circuit board 11 and a main surface 11a of the first circuit board 11.
- a member 13 and a second circuit member 16 having a second electrode 15 formed on the main surface 14a of the second circuit board 14 and the second circuit board 14 are prepared.
- the first circuit member 13 and the second circuit member 16 are arranged so that the first electrode 12 and the second electrode 15 face each other, and the first circuit member 13 and the second circuit member 16 are arranged.
- the adhesive film 1 is arranged between the circuit member 16 and the circuit member 16.
- the adhesive film 1 is laminated on the first circuit member 13 so that the first adhesive layer 2 side faces the main surface 11a of the first circuit member 13.
- the adhesive film 1 is laminated so that the first electrode 12 on the first circuit board 11 and the second electrode 15 on the second circuit board 14 face each other.
- the second circuit member 16 is arranged on the circuit member 13.
- the adhesive film 1 may be laminated on the second circuit member 16 so that the first adhesive layer 2 side faces the main surface 14a of the second circuit member 16. Good.
- the adhesive film 1 is laminated so that the first electrode 12 on the first circuit board 11 and the second electrode 15 on the second circuit board 14 face each other.
- the first circuit member 13 is arranged on the circuit member 16.
- the first circuit member 13 and the second circuit member 16 are heated while heating the first circuit member 13, the adhesive film 1 and the second circuit member 16.
- the first circuit member 13 and the second circuit member 16 are thermocompression bonded to each other.
- the second adhesive layer flows so as to fill the gap between the second electrodes 15 and 15, and is cured by the above heating.
- the first electrode 12 and the second electrode 15 are electrically connected to each other via the conductive particles 4, and the first circuit member 13 and the second circuit member 16 are adhered to each other.
- the circuit connection structure 10 shown in 3 is obtained.
- the conductive particles 4 are fixed in the first adhesive layer 2, and the first adhesive layer 2 hardly flows during the thermocompression bonding. , It becomes easy to be captured between the first electrode 12 and the second electrode 15 facing each other, and as a result, the connection resistance between the first electrode 12 and the second electrode 15 is reduced. Therefore, a circuit connection structure having excellent connection reliability can be obtained.
- the second curable composition contains a photocurable composition
- the first circuit is formed by performing pressurization and light irradiation, or pressurization and heating and light irradiation instead of thermocompression bonding by heating.
- the member 13 and the second circuit member 16 may be connected.
- FIG. 5 is a perspective view showing an adhesive film accommodating set of one embodiment.
- the adhesive film accommodating set 20 includes an adhesive film 1 for circuit connection, a reel 21 around which the adhesive film 1 is wound, and an accommodating member 22 accommodating the adhesive film 1 and the reel 21. And.
- the adhesive film 1 is, for example, in the form of a tape.
- the tape-shaped adhesive film 1 is produced, for example, by cutting a sheet-shaped raw fabric into a long length with a width suitable for the intended use.
- a base material may be provided on one surface of the adhesive film 1.
- a base material such as the PET film described above can be used.
- the reel 21 has a first side plate 24 having a winding core 23 around which the adhesive film 1 is wound, and a second side plate 25 arranged so as to face the first side plate 24 with the winding core 23 interposed therebetween. Be prepared.
- the first side plate 24 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 24.
- the winding core 23 of the first side plate 24 is a portion around which the adhesive film 1 is wound.
- the winding core 23 is made of, for example, plastic, and has an annular shape having a thickness similar to the width of the adhesive film 1.
- the winding core 23 is fixed to the inner side surface of the first side plate 24 so as to surround the opening of the first side plate 24.
- a desiccant container containing a desiccant may be fitted in the shaft hole 26.
- the second side plate 25 is a disk made of, for example, plastic, and the central portion of the second side plate 25 has a circular cross section having the same diameter as the opening of the first side plate 24. The opening is provided.
- the accommodating member 22 has a bag shape, for example, and accommodates the adhesive film 1 and the reel 21.
- the accommodating member 22 has an insertion port 27 for accommodating (inserting) the adhesive film 1 and the reel 21 inside the accommodating member 22.
- the accommodating member 22 has a visual recognition portion 28 that makes the inside of the accommodating member 22 visible from the outside.
- the accommodating member 22 shown in FIG. 5 is configured such that the entire accommodating member 22 serves as a visual recognition portion 28.
- the visual recognition unit 28 has transparency to visible light. For example, when the light transmittance in the visual recognition unit 28 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 28 to a predetermined size and measuring the light transmittance of the sample with an ultraviolet-visible spectrophotometer.
- the accommodating member 22 has such a visual recognition portion 28, various information such as a product name, a lot number, and an expiration date affixed to the reel 21 inside the accommodating member 22 can be confirmed from the outside of the accommodating member 22. 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 28 is 10% or less. Since the transmittance of the light having a wavelength of 365 nm in the visual recognition unit 28 is 10% or less, the light incident from the outside to the inside of the accommodating member 22 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 2 can be suppressed. As a result, it is possible to suppress the occurrence of problems such as easy peeling between the circuit member and the circuit connection portion in a high temperature and high humidity environment and a decrease in the effect of reducing the connection resistance of the adhesive film.
- the transmittance of light having a wavelength of 365 nm in the visual recognition unit 28 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 28 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 28 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 28 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 visual recognition unit 28 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 28 may have a laminated structure formed by laminating a plurality of layers having different light transmission characteristics. In this case, each layer constituting the visual recognition unit 28 may be made of the above-mentioned material.
- the insertion port 27 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 22 before closing the insertion port 27. It can be expected that the humidity inside the accommodating member 22 will be reduced from the initial stage of accommodating and that air will be prevented from entering from the outside. When the inner surface of the accommodating member 22 and the reel 21 are in close contact with each other, the inner surface of the accommodating member 22 and the surface of the reel 21 rub against each other due to vibration during transportation to generate foreign matter, and the side plates 24 and 25 of the reel 21 Can prevent scratches on the outer surface of the reel.
- 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.
- 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.
- ⁇ 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 tetrabutoxytitanate as a catalyst was added. 0.02 parts by mass was charged. 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), and the mixture was cooled to room temperature. As a result, a white precipitate was precipitated.
- polyester polyol After the obtained polyester polyol was sufficiently dried, it was dissolved in MEK (methyl ethyl ketone) and placed in a four-necked flask equipped with a stirrer, a dropping funnel, a reflux cooler and a nitrogen gas introduction tube. 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 in an amount of 50 parts by mass with respect to 100 parts by mass of the polyester polyol was added. It was dissolved in MEK, charged with a dropping funnel, and stirred at 80 ° C. for 4 hours to obtain the desired polyester urethane resin.
- MEK methyl ethyl ketone
- 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 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)
- D1 Conductive particles (thermoplastic resin) prepared as described above
- E1 Polyester urethane
- the layer made of the first curable composition 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. As a result, the first curable composition was cured to form the first adhesive layer.
- a first adhesive film having a first adhesive layer on the PET film was obtained.
- Each of the obtained adhesive films 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) After casting with a resin composition consisting of 10 g of an agent, refine tech Co., Ltd., 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.) ) was used to measure the thickness of each layer.
- SEM scanning electron microscope
- Measurement results (shortest distance from the surface of the adhesive film on the side of the first adhesive layer to the conductive particles, the thickness of each of the substantially thickest part and the substantially thinnest part of the first adhesive layer, and the second adhesion.
- Tables 2 and 3 show the thickness of the substantially thickest portion of the agent layer and the total thickness of the first adhesive layer and the second adhesive layer).
- the thickness of the substantially thickest portion of the first adhesive layer means the thickness at the position where the thickness of the first adhesive layer is substantially maximum in the non-existent region where the conductive particles do not exist.
- the thickness of the substantially thinnest portion of the first adhesive layer means the thickness at a position where the thickness of the first adhesive layer is substantially minimized in the absence region where the conductive particles do not exist.
- the thickness of the substantially thickest portion of the second adhesive layer means the thickness at the position where the thickness of the second adhesive layer is substantially maximum in the absence region where the conductive particles do not exist. Further, the ratio of the thickness of the first adhesive layer to the average particle size of the conductive particles calculated from the measurement results, and the second to the total thickness of the first adhesive layer and the second adhesive layer. The ratio of the thickness of the substantially thickest part of the adhesive layer is also shown in Tables 2 and 3.
- 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 arranged on the glass substrate so that the surface of the circuit connection adhesive film on the first adhesive layer side faced the glass substrate.
- the particle flow state of the exuded portion of the circuit connection adhesive film was evaluated using a microscope (trade name: ECLIPSE L200, manufactured by Nikon Corporation). Specifically, the produced circuit connection structure was observed from the glass substrate side with a microscope, and the particle state of the portion exuded outside the width of the circuit connection adhesive film was evaluated in three stages. The state where the particles hardly move and there are no particles in the exuded part 1, the state where the particles move a little but the particles are not connected to each other 2, the state where the particles flow and the particles are connected to each other It was set to 3.
- connection resistance value For the examples and comparative examples in which the evaluation of the fluidity of the conductive particles was 1 or 2 (the flow of the conductive particles is suppressed), the connection resistance value was also evaluated. Specifically, with respect to the obtained circuit connection structure, the connection resistance value between the opposing electrodes immediately after the connection and after the high temperature and high humidity test was measured with a multimeter. The high temperature and high humidity test was carried out by leaving the product in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 200 hours. The connection resistance value was determined as the average value of 16 resistance points between the opposing electrodes.
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Abstract
Description
図1は、一実施形態の回路接続用接着剤フィルムを示す模式断面図である。図1に示すように、回路接続用接着剤フィルム1(以下、単に「接着剤フィルム1」ともいう。)は、第1の接着剤層2と、第1の接着剤層2上に積層された第2の接着剤層3と、を備える。
第1の接着剤層2は、例えば、第1の硬化性組成物の硬化物からなる。第1の硬化性組成物は、光硬化性組成物であってよく、熱硬化性組成物であってよく、光・熱硬化性組成物(光硬化性及び熱硬化性の両方を有する組成物)であってもよい。第1の硬化性組成物は、例えば、(A)重合性化合物(以下、「(A)成分」ともいう。)、(B)重合開始剤(以下、「(B)成分」ともいう。)、及び(C)導電粒子4(以下、「(C)成分」ともいう。)を含有する。
(A)成分は、例えば、光(例えば紫外光)の照射又は加熱によって重合開始剤(光重合開始剤又は熱重合開始剤)が発生させたラジカル、カチオン又はアニオンにより重合する化合物である。(A)成分は、モノマー、オリゴマー又はポリマーのいずれであってもよい。(A)成分として、一種の化合物を単独で用いてよく、複数種の化合物を組み合わせて用いてもよい。
(B)成分は、150~750nmの範囲内の波長を含む光、好ましくは254~405nmの範囲内の波長を含む光、更に好ましくは365nmの波長を含む光(例えば紫外光)の照射によってラジカル、カチオン又はアニオンを発生する光重合開始剤(光ラジカル重合開始剤、光カチオン重合開始剤又は光アニオン重合開始剤)であってよく、熱によってラジカル、カチオン又はアニオンを発生する熱重合開始剤(熱ラジカル重合開始剤、熱カチオン重合開始剤又は熱アニオン重合開始剤)であってよい。(B)成分は、高温高湿環境下における接続抵抗の上昇を更に抑制できる観点から、ラジカル重合開始剤(光ラジカル重合開始剤又は熱ラジカル重合開始剤)であることが好ましい。(B)成分として、一種の化合物を単独で用いてよく、複数種の化合物を組み合わせて用いてもよい。例えば、第1の硬化性組成物が(B)成分として光重合開始剤及び熱重合開始剤の両方を含有していてもよい。
(C)成分は、導電性を有する粒子であれば特に制限されず、Au、Ag、Ni、Cu、はんだ等の金属で構成された金属粒子、導電性カーボンで構成された導電性カーボン粒子などであってよい。(C)成分は、非導電性のガラス、セラミック、プラスチック(ポリスチレン等)などを含む核と、上記金属又は導電性カーボンを含み、核を被覆する被覆層とを備える被覆導電粒子であってもよい。これらの中でも、熱溶融性の金属で形成された金属粒子、又はプラスチックを含む核と、金属又は導電性カーボンを含み、核を被覆する被覆層とを備える被覆導電粒子が好ましく用いられる。この場合、第1の硬化性組成物の硬化物を加熱又は加圧により変形させることが容易であるため、電極同士を電気的に接続する際に、電極と(C)成分との接触面積を増加させ、電極間の導電性をより向上させることができる。
第1の硬化性組成物は、(A)成分、(B)成分及び(C)成分以外のその他の成分を更に含有していてよい。その他の成分としては、例えば、熱可塑性樹脂、カップリング剤及び充填材が挙げられる。これらの成分は、第1の接着剤層2に含有されていてもよい。
第2の接着剤層3は、例えば、第2の硬化性組成物である第2の接着剤成分6からなる。第2の硬化性組成物は、例えば、(a)重合性化合物(以下、(a)成分ともいう。)及び(b)重合開始剤(以下、(b)成分ともいう。)を含有する。第2の硬化性組成物は、(b)成分として熱重合開始剤を含有する熱硬化性組成物であってよく、(b)成分として光重合開始剤を含有する光硬化性組成物であってもよく、光・熱硬化性組成物(光硬化性及び熱硬化性の両方を有する組成物)であってもよい。第2の接着剤層3を構成する第2の硬化性組成物は、回路接続時に流動可能な未硬化の硬化性組成物である。
(a)成分は、例えば、光(例えば紫外光)の照射又は加熱によって重合開始剤(光重合開始剤又は熱重合開始剤)が発生させたラジカル、カチオン又はアニオンにより重合する化合物である。(a)成分としては、(A)成分として例示した化合物を用いることができる。(a)成分は、低温短時間での接続が容易となり、接続抵抗の低減効果が更に向上し、接続信頼性により優れる観点から、ラジカルにより反応するラジカル重合性基を有するラジカル重合性化合物であることが好ましい。(a)成分における好ましいラジカル重合性化合物の例及び好ましいラジカル重合性化合物の組み合わせは、(A)成分と同様である。(a)成分がラジカル重合性化合物であり、且つ、第1の接着剤層における(B)成分が光ラジカル重合開始剤である場合、接着剤フィルムを後述する収容部材に収容することで、接着剤フィルムの保管時又は運搬時における第2の硬化性組成物の硬化が顕著に抑制される傾向がある。
(b)成分としては、(B)成分として例示した重合開始剤と同様の重合開始剤を用いることができる。(b)成分は、ラジカル重合開始剤であることが好ましい。(b)成分における好ましいラジカル重合開始剤の例は、(B)成分と同様である。(b)成分として、一種の化合物を単独で用いてよく、複数種の化合物を組み合わせて用いてもよい。第2の硬化性組成物は、(b)成分として、好ましくは、光重合開始剤及び熱重合開始剤のうち少なくとも一方を含有し、回路接続が更に容易となる観点から、より好ましくは熱重合開始剤を含有し、更に好ましくは熱重合開始剤のみを含有する。
第2の硬化性組成物は、(a)成分及び(b)成分以外のその他の成分を更に含有していてよい。その他の成分としては、例えば、熱可塑性樹脂、カップリング剤、充填材、軟化剤、促進剤、劣化防止剤、着色剤、難燃化剤、チキソトロピック剤等が挙げられる。その他の成分の詳細は、第1の接着剤層2におけるその他の成分の詳細と同じである。
本実施形態の回路接続用接着剤フィルム1の製造方法は、例えば、上述した第1の接着剤層2を用意する用意工程(第1の用意工程)と、第1の接着剤層2上に上述した第2の接着剤層3を積層する積層工程と、を備える。回路接続用接着剤フィルム1の製造方法は、第2の接着剤層3を用意する用意工程(第2の用意工程)を更に備えていてもよい。
以下、回路接続材料として上述した回路接続用接着剤フィルム1を用いた回路接続構造体及びその製造方法について説明する。
図5は、一実施形態の接着剤フィルム収容セットを示す斜視図である。図5に示すように、接着剤フィルム収容セット20は、回路接続用接着剤フィルム1と、該接着剤フィルム1が巻き付けられたリール21と、接着剤フィルム1及びリール21を収容する収容部材22と、を備える。
図5に示す収容部材22は、収容部材22の全体が視認部28となるように構成されている。
攪拌機、温度計、塩化カルシウム乾燥管を有する還流冷却管、及び、窒素ガス導入管を備えた反応容器に、ポリ(1,6-ヘキサンジオールカーボネート)(商品名:デュラノール T5652、旭化成ケミカルズ株式会社製、数平均分子量1000)2500質量部(2.50mol)と、イソホロンジイソシアネート(シグマアルドリッチ社製)666質量部(3.00mol)とを3時間かけて均一に滴下した。次いで、反応容器に充分に窒素ガスを導入した後、反応容器内を70~75℃に加熱して反応させた。次に、反応容器に、ハイドロキノンモノメチルエーテル(シグマアルドリッチ社製)0.53質量部(4.3mmol)と、ジブチルスズジラウレート(シグマアルドリッチ社製)5.53質量部(8.8mmol)とを添加した後、2-ヒドロキシエチルアクリレート(シグマアルドリッチ社製)238質量部(2.05mol)を加え、空気雰囲気下70℃で6時間反応させた。これにより、ポリウレタンアクリレート(UA1)を得た。ポリウレタンアクリレート(UA1)の重量平均分子量は15000であった。なお、重量平均分子量は、下記の条件に従って、ゲル浸透クロマトグラフ(GPC)より標準ポリスチレンによる検量線を用いて測定した。
(測定条件)
装置:東ソー株式会社製 GPC-8020
検出器:東ソー株式会社製 RI-8020
カラム:日立化成株式会社製 Gelpack GLA160S+GLA150S
試料濃度:120mg/3mL
溶媒:テトラヒドロフラン
注入量:60μL
圧力:2.94×106Pa(30kgf/cm2)
流量:1.00mL/min
ポリスチレン粒子の表面上に、層の厚さが0.2μmとなるようにニッケルからなる層を形成した。このようにして、平均粒径4μm、最大粒径4.5μm、比重2.5の導電粒子を得た。
攪拌機、温度計、コンデンサー、真空発生装置及び窒素ガス導入管が備え付けられたヒーター付きステンレス製オートクレーブに、イソフタル酸48質量部及びネオペンチルグリコール37質量部を投入し、更に、触媒としてのテトラブトキシチタネート0.02質量部を投入した。次いで、窒素気流下220℃まで昇温し、そのまま8時間攪拌した。その後、大気圧(760mmHg)まで減圧し、室温まで冷却した。これにより、白色の沈殿物を析出させた。次いで、白色の沈殿物を取り出し、水洗した後、真空乾燥することでポリエステルポリオールを得た。得られたポリエステルポリオールを十分に乾燥した後、MEK(メチルエチルケトン)に溶解し、攪拌機、滴下漏斗、還流冷却機及び窒素ガス導入管を取り付けた四つ口フラスコに投入した。また、触媒としてジブチル錫ラウレートをポリエステルポリオール100質量部に対して0.05質量部となる量投入し、ポリエステルポリオール100質量部に対して50質量部となる量の4,4’-ジフェニルメタンジイソシアネートをMEKに溶解して滴下漏斗で投入し、80℃で4時間攪拌することで目的とするポリエステルウレタン樹脂を得た。
以下に示す成分を表1に示す配合量(質量部)で混合し、第1の硬化性組成物のワニス及び第2の硬化性組成物のワニスを調製した。
A1:ジシクロペンタジエン型ジアクリレート(商品名:DCP-A、東亞合成株式会社製)
A2:上述のとおり合成したポリウレタンアクリレート(UA1)
A3:2-メタクリロイルオキシエチルアシッドフォスフェート(商品名:ライトエステルP-2M、共栄社化学株式会社製)
(光重合開始剤)
B1:1,2-オクタンジオン,1-[4-(フェニルチオ)フェニル]-,2-(o-ベンゾイルオキシム)(商品名:Irgacure(登録商標)OXE01、BASF社製)
(熱重合開始剤)
C1:ベンゾイルパーオキサイド(商品名:ナイパーBMT-K40、日油株式会社製)
(導電粒子)
D1:上述のとおり作製した導電粒子
(熱可塑性樹脂)
E1:上述のとおり合成したポリエステルウレタン樹脂
E2:フェノキシ樹脂(商品名:PKHC、ユニオンカーバイド社製)
(カップリング剤)
F1:3-メタクリロキシプロピルトリメトキシシラン(商品名:KBM503、信越化学工業株式会社製)
(充填材)
G1:シリカ微粒子(商品名:R104、日本アエロジル株式会社製、平均粒径(一次粒径):12nm)
(溶剤)
H1:メチルエチルケトン
[第1の接着剤フィルムの作製]
第1の硬化性組成物のワニスを、厚さ50μmのPETフィルム上に塗工装置を用いて塗布した。次いで、70℃、3分間の熱風乾燥を行い、PETフィルム上に第1の硬化性組成物からなる層を形成した。このとき、ワニスにおける溶剤H1(メチルエチルケトン)の含有量を0~300質量部の範囲で調整することにより、得られる第1の接着剤層の厚さを表2,3に示すとおりに調整した。
次に、第1の硬化性組成物からなる層に対し、メタルハライドランプを用いて積算光量が1500mJ/cm2となるように光照射を行い、重合性化合物を重合させた。これにより、第1の硬化性組成物を硬化させ、第1の接着剤層を形成した。以上の操作により、PETフィルム上に第1の接着剤層を備える第1の接着剤フィルムを得た。
第2の硬化性組成物のワニスを、厚さ50μmのPETフィルム上に塗工装置を用いて塗布した。次いで、70℃、3分間の熱風乾燥を行い、PETフィルム上に第2の接着剤層(第2の硬化性組成物からなる層)を形成した。このとき、ワニスにおける溶剤H1(メチルエチルケトン)の含有量を0~100質量部の範囲で調整することにより、得られる第2の接着剤層の厚さを表2,3に示すとおりに調整した。以上の操作により、PETフィルム上に第2の接着剤層を備える第2の接着剤フィルムを得た。
第1の接着剤フィルムと第2の接着剤フィルムとを、基材であるPETフィルムと共に40℃で加熱しながら、ロールラミネータでラミネートした。これにより、第1の接着剤層と第2の接着剤層とが積層された二層構成の回路接続用接着剤フィルムを備える、基材付き回路接続用接着剤フィルムを作製した。
第2の硬化性組成物のワニスを用いて、厚さ1μmの接着剤層(第3の接着剤層)を作製した。次に、実施例2の接着剤フィルムにおいて、第1の接着剤層の第2の接着剤層と反対側の面上に第3の接着剤層を更にラミネートして、接着剤フィルムを得た。得られた接着剤フィルムにおける各層の厚み等を上記と同様にして測定した。結果を表3に示す。
作製した回路接続用接着剤フィルムを介して、ピッチ25μmのCOF(FLEXSEED社製)と、ガラス基板上に非結晶酸化インジウム錫(ITO)からなる薄膜電極(高さ:1200Å)を備える、薄膜電極付きガラス基板(ジオマテック社製)とを、熱圧着装置(加熱方式:コンスタントヒート型、株式会社太陽機械製作所製)を用いて、170℃、6MPaで4秒間の条件で加熱加圧を行って幅1mmにわたり接続し、回路接続構造体(接続構造体)を作製した。なお、接続の際には、回路接続用接着剤フィルムにおける第1の接着剤層側の面がガラス基板と対向するように、回路接続用接着剤フィルムをガラス基板上に配置した。
得られた回路接続構造体について、回路接続用接着剤フィルムの染み出し部分の粒子流動状態を顕微鏡(商品名:ECLIPSE L200、株式会社ニコン製)を用いて評価した。具体的には、作製した回路接続構造体をガラス基板側から、顕微鏡にて観察し、回路接続用接着剤フィルムの幅よりも外側に染み出した部分の粒子状態を3段階で評価した。粒子がほとんど動かず、染み出し部分に粒子がない状態を1、多少粒子が動いているが、粒子が互いに連結していない状態を2、粒子が流動し、粒子が互いに連結している状態を3とした。
上記の導電粒子の流動性の評価において1又は2であった(導電粒子の流動が抑制されている)実施例及び比較例については、接続抵抗値の評価も実施した。具体的には、得られた回路接続構造体について、接続直後、及び、高温高湿試験後の対向する電極間の接続抵抗値を、マルチメーターで測定した。高温高湿試験は、85℃、85%RHの恒温恒湿槽に200時間放置することにより行った。接続抵抗値は、対向する電極間の抵抗16点の平均値として求めた。
Claims (8)
- 導電粒子を含有する第1の接着剤層と、
前記第1の接着剤層上に積層された第2の接着剤層と、を備える回路接続用接着剤フィルムであって、
前記接着剤フィルムの前記第1の接着剤層側の表面から前記導電粒子の表面までの最短距離が0μmを超え1μm以下であり、
前記導電粒子の平均粒径に対する前記第1の接着剤層の厚さの比が10%以上80%以下であり、
前記第1の接着剤層及び前記第2の接着剤層の合計厚さに対する前記第2の接着剤層の厚さの比が96%未満である、回路接続用接着剤フィルム。 - 前記第1の接着剤層は第1の硬化性組成物の硬化物からなり、
前記第1の硬化性組成物は、ラジカル重合性基を有するラジカル重合性化合物を含有する、請求項1に記載の回路接続用接着剤フィルム。 - 前記第2の接着剤層は第2の硬化性組成物からなり、
前記第2の硬化性組成物は、ラジカル重合性基を有するラジカル重合性化合物を含有する、請求項1又は2に記載の回路接続用接着剤フィルム。 - 導電粒子を含有する第1の接着剤層と、前記第1の接着剤層上に積層された第2の接着剤層と、を備える回路接続用接着剤フィルムの製造方法であって、
前記第1の接着剤層を用意する用意工程と、
前記第1の接着剤層上に、第2の硬化性組成物からなる前記第2の接着剤層を積層する積層工程と、を備え、
前記用意工程は、導電粒子を含有する第1の硬化性組成物からなる層に対して光照射又は加熱を行うことにより前記第1の硬化性組成物を硬化させ、前記第1の接着剤層を得る硬化工程を含み、
前記接着剤フィルムの前記第1の接着剤層側の表面から前記導電粒子の表面までの最短距離が0μmを超え1μm以下であり、
前記導電粒子の平均粒径に対する前記第1の接着剤層の厚さの比が10%以上80%以下であり、
前記第1の接着剤層及び前記第2の接着剤層の合計厚さに対する前記第2の接着剤層の厚さの比が96%未満である、回路接続用接着剤フィルムの製造方法。 - 前記第1の硬化性組成物は、ラジカル重合性基を有するラジカル重合性化合物を更に含有する、請求項4に記載の回路接続用接着剤フィルムの製造方法。
- 前記第2の硬化性組成物は、ラジカル重合性基を有するラジカル重合性化合物を含有する、請求項4又は5に記載の回路接続用接着剤フィルムの製造方法。
- 第1の電極を有する第1の回路部材と、第2の電極を有する第2の回路部材との間に、請求項1~3のいずれか一項に記載の回路接続用接着剤フィルムを介在させ、前記第1の回路部材及び前記第2の回路部材を熱圧着して、前記第1の電極及び前記第2の電極を互いに電気的に接続する工程を備える、回路接続構造体の製造方法。
- 請求項1~3のいずれか一項に記載の回路接続用接着剤フィルムと、該接着剤フィルムを収容する収容部材と、を備え、
前記収容部材は、前記収容部材の内部を外部から視認可能とする視認部を有し、
前記視認部における波長365nmの光の透過率は10%以下である、接着剤フィルム収容セット。
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