WO2012169535A1 - フィルム状回路接続材料及び回路接続構造体 - Google Patents
フィルム状回路接続材料及び回路接続構造体 Download PDFInfo
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- WO2012169535A1 WO2012169535A1 PCT/JP2012/064572 JP2012064572W WO2012169535A1 WO 2012169535 A1 WO2012169535 A1 WO 2012169535A1 JP 2012064572 W JP2012064572 W JP 2012064572W WO 2012169535 A1 WO2012169535 A1 WO 2012169535A1
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- conductive particles
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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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- 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
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
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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
- C09J175/06—Polyurethanes from polyesters
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/14—Structural association of two or more 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
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0221—Insulating particles having an electrically conductive coating
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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
Definitions
- the present invention relates to a film-like circuit connection material and a circuit connection structure.
- an anisotropic conductive adhesive film is known as a film-like circuit connecting material that is interposed between circuit electrodes facing each other and is used to electrically connect electrodes in a pressing direction by heating and pressing.
- an anisotropic conductive adhesive film obtained by dispersing conductive particles in an epoxy adhesive or an acrylic adhesive is known.
- Such an anisotropic conductive adhesive film is mainly composed of a TCP (Tape Carrier Package) or COF (Chip On Flex) on which a semiconductor for driving a liquid crystal display (hereinafter referred to as “LCD”) is mounted, and an LCD panel. It is widely used for electrical connection between a TCP or COF and a printed wiring board.
- a film-like circuit connecting material is used for bonding a wiring member made of an insulating organic substance or glass, or a wiring member made of at least a part of the surface of which is made of at least one of silicon nitride, silicone resin, and polyimide resin.
- Patent Document 10 In order to reduce the internal stress based on the difference in the thermal expansion coefficient after adhesion (see, for example, Patent Document 10), and to improve the adhesion by incorporating silicone particles in the rubber particles, the rubber particles are dispersed in the film-like circuit connection material
- the method of making it known is known (for example, refer to Patent Document 11).
- indium-tin oxide is used instead of an indium-tin oxide (ITO) electrode as a circuit electrode (thin film electrode) provided on a glass substrate.
- Oxide oxide
- IZO electrode from the viewpoint of reducing the connection resistance between the circuit electrodes, instead of the film-like circuit connection material in which the conductive particles covered with the outermost layer made of Au or the like are dispersed, Ni, Ni alloy or Ni A film-like circuit connecting material in which conductive particles covered with an outermost layer containing an oxide or the like are dispersed has been studied.
- TFT-LCD it is common to form a metal circuit such as Mo or Al as the base of the above-mentioned thin film electrode.
- a metal circuit such as Mo or Al
- the routing of the thin film circuit has become very complicated. For this reason, especially in the panel using the IZO electrode, the circuit resistance is reduced. The resulting electrode burn (burnt phenomenon) may occur. Therefore, a low-resistance film-like circuit connection material in which conductive particles covered with an outermost layer containing Ni, Ni alloy, Ni oxide, etc. are dispersed has attracted attention.
- a CCD camera or a laser sensor is installed in the production facility in order to check whether or not the film-like circuit connecting material is stuck at a predetermined position on the substrate.
- a film-like circuit connecting material in which conductive particles covered with an outermost layer containing Ni, Ni alloy, Ni oxide, etc. are dispersed, there is a problem that visibility when using a laser sensor, for example, is lowered. ing.
- the transparency of the film-like circuit connecting material is high, or when the thickness of the film-like circuit connecting material is thin, not only the laser sensor but also the CCD camera tends to lack visibility.
- the present invention has been made in order to solve the above-mentioned problems, and has a film-like circuit connection material that has excellent insulation and can ensure visibility by a sensor while reducing the connection resistance between circuit electrodes, and uses the same.
- the main object is to provide a circuit connection structure.
- the present invention relates to a film-like circuit connecting material having an adhesive layer that is used to electrically connect circuit electrodes to be interposed between opposing circuit electrodes.
- the adhesive layer comprises (a) a thermoplastic resin, (b) a curable material, (c) a curing agent, and (d) an adhesive component containing a dye, a plastic core, and a metal that covers the plastic core.
- the outermost layer of the metal layer is a layer formed by plating (metal plating) containing at least one selected from the group consisting of Ni, Ni alloy and Ni oxide, and has an average particle size And conductive particles having a size of 2.0 to 3.5 ⁇ m.
- the average particle diameter of the conductive particles is 2.0 ⁇ m to 3.5 ⁇ m, even in a high-definition circuit electrode, a short circuit between the circuit electrodes can be suppressed.
- the conductive particles having such an average particle diameter with a dye or the like, the color difference between the portion where the film-like circuit connecting material is attached and the portion where the film-like circuit connecting material is not attached is increased while reducing the connection resistance. As a result, the visibility can be ensured without depending on the type of sensor, and the sticking state can be easily recognized.
- the number of conductive particles in the film-like circuit connecting material is preferably 2000 to 15000 / mm 2 when viewed from the thickness direction of the adhesive layer. In this case, it is possible to secure a sufficient contact area to obtain a good connection resistance while suppressing the cost. Moreover, deterioration of insulation resistance can be suppressed.
- the circuit connection structure according to the present invention includes an adhesive layer of the film-like circuit connection material between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode.
- the film-like circuit connecting material is obtained by electrically connecting the first circuit electrode and the second circuit electrode by heating and pressing the film-like circuit connecting material.
- connection resistance between the circuit electrodes can be reduced without depending on the type of the circuit electrodes.
- the visibility can be ensured without depending on the type of sensor, and the sticking state can be easily recognized, so that the connection reliability can be secured.
- the present invention sufficient visibility by the sensor can be ensured while reducing the connection resistance between the circuit electrodes.
- it is easy to check the presence or absence of the adhesive layer even when the film circuit connection material is wound in a reel shape, and it is easy to check whether the circuit connection material is flowing properly after circuit connection.
- the present invention has advantageous effects.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a film-like circuit connecting material.
- the film-like circuit connecting material 1 shown in FIG. 1 has an adhesive layer (anisotropic conductive adhesive layer) 61 containing an adhesive component 3 and conductive particles 5.
- the film-like circuit connecting material (adhesive layer) 1 is used to electrically connect circuit electrodes by interposing between facing circuit electrodes when a circuit connecting structure as described later is manufactured.
- This film-like circuit connection material 1 is used for, for example, FOG (Film on Glass) connection between a TCP or COF on which a semiconductor for driving an LCD is mounted and an LCD panel, or FOG connection between a TCP or COF and a printed wiring board. .
- the film-like circuit connecting material 1 is also useful for FOP (Film on Plastic) connection.
- the adhesive component 3 contains (a) a thermoplastic resin, (b) a curable substance, (c) a curing agent, and (d) a dye.
- thermoplastic resin is, for example, polystyrene, polyethylene, polyvinyl butyral, polyvinyl formal, polyimide, polyamide, polyester, polyvinyl chloride, polyphenylene oxide, urea resin, melamine resin, phenol resin, xylene resin, epoxy resin, polyisocyanate. It contains at least one selected from the group consisting of resins, phenoxy resins, polyimide resins, and polyester urethane resins.
- thermoplastic resin preferably 10,000 or more. Further, the weight average molecular weight of the thermoplastic resin is preferably less than 1,000,000 because good mixing with other components can be obtained.
- the weight average molecular weight in the present embodiment is a value determined by gel permeation chromatography (GPC) analysis under the following conditions and converted by using a standard polystyrene calibration curve.
- the GPC conditions are as follows. Equipment used: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name) Detector: L-3300RI (trade name, manufactured by Hitachi, Ltd.) Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran Measurement temperature: 40 ° C. Flow rate: 1.75 ml / min
- thermoplastic resin is preferably 30 parts by mass to 80 parts by mass, and more preferably 35 parts by mass to 70 parts by mass with respect to 100 parts by mass of the adhesive component 3.
- the curable substance may be, for example, (b1) a radical polymerizable substance having a functional group that is polymerized by radicals.
- radical polymerizable substance examples include acrylates (including corresponding methacrylates, the same applies hereinafter) and maleimide compounds.
- acrylate examples include urethane acrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, 2-hydroxy -1,3-diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, Tricyclodecanyl acrylate, bis (acryloxyethyl) isocyanurate, ⁇ -caprolactone modified tris (acryloxyethyl) iso Cyanurate, and it may be at least one compound selected from the group consisting of tris (acryloyloxyethyl) isocyanurate.
- the maleimide compound preferably has two or more maleimide groups in the molecule.
- maleimide compounds include 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N, N′-P-phenylenebismaleimide, and N, N′-m-toluylenebis.
- the radical polymerizable substance is preferably an acrylate, more preferably a urethane acrylate or a urethane methacrylate, from the viewpoint of improving adhesiveness.
- a radically polymerizable substance can be used alone or in combination of two or more.
- the adhesive component 3 preferably contains at least a radical polymerizable substance having a viscosity at 25 ° C. of 100,000 to 1,000,000 mPa ⁇ s, and more preferably contains a radical polymerizable substance having a viscosity of 100,000 to 500,000 mPa ⁇ s.
- the viscosity of the radical polymerizable substance can be measured using a commercially available E-type viscometer.
- the content of the radical polymerizable substance is preferably 20 to 70 parts by mass, more preferably 30 to 65 parts by mass with respect to 100 parts by mass of the adhesive component.
- the radical polymerizable substance is crosslinked with a curing agent (organic peroxide) in order to improve heat resistance, and radical polymerization showing Tg of 100 ° C. or more alone. It is particularly preferable to further contain a functional substance.
- a radical polymerizable substance a compound having a dicyclopentenyl group, a tricyclodecanyl group and / or a triazine ring can be used. Among these, a radically polymerizable substance having a tricyclodecanyl group or a triazine ring is preferably used.
- the adhesive component may appropriately contain a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone as necessary.
- the radical polymerizable substance preferably further contains a radical polymerizable substance having a phosphate ester structure in addition to the radical polymerizable substance.
- the radically polymerizable substance having a phosphate ester structure is obtained, for example, as a reaction product of phosphoric anhydride and 2-hydroxyl (meth) acrylate.
- Specific examples of the radical polymerizable compound having a phosphate structure include 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, and the like. These can be used individually by 1 type or in combination of 2 or more types.
- the content of the radical polymerizable substance having a phosphate ester structure is 0.1 to 10 parts by mass with respect to 100 parts by mass of the adhesive component from the viewpoint of improving the adhesive strength with the surface of an inorganic substance such as a metal. It is preferably 0.5 parts by mass to 5 parts by mass.
- the curable substance may be (b2) a thermosetting resin.
- the thermosetting resin is preferably an epoxy resin.
- the epoxy resin various epoxy compounds having two or more epoxy groups (glycidyl groups) in one molecule are used alone or in combination of two or more.
- the epoxy resin is, for example, a bisphenol type epoxy resin derived from epichlorohydrin and bisphenol A, bisphenol F and / or bisphenol AD, an epoxy novolac resin derived from epichlorohydrin and phenol novolac or cresol novolac, and a skeleton containing a naphthalene ring.
- the epoxy resin is preferably a high-purity product in which impurity ions (Na + , Cl- and the like), hydrolyzable chlorine and the like are reduced to 300 ppm or less in order to prevent electron migration.
- the curing agent is appropriately selected according to the intended connection temperature, connection time, adherend, and the like.
- a compound (free radical generator) that generates an active radical by at least one treatment of heating and light irradiation, such as a peroxide compound (organic peroxide), an azo compound, or a photoinitiator is used as a curing agent. Can be used.
- the organic peroxide has a half-life temperature of 40 ° C or higher and a half-life temperature of 1 minute is 180 ° C or lower. preferable. More preferably, the organic peroxide has a half-life of 10 hours at a temperature of 60 ° C. or higher and a half-life of 1 minute at a temperature of 170 ° C. or lower.
- the organic peroxide preferably has a chlorine ion and organic acid content of 5000 ppm or less in order to prevent corrosion of the circuit electrode of the circuit member. Furthermore, it is more preferable that the organic acid generated after the thermal decomposition of the organic peroxide is small.
- the organic peroxide may be at least one selected from the group consisting of diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, and hydroperoxide, for example.
- peroxyesters dialkyl peroxides, and hydroperoxides from the viewpoint of suppressing corrosion of connection terminals of circuit members, and from the viewpoint of obtaining high reactivity, it is selected from peroxyesters. More preferably.
- diacyl peroxide examples include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide , Benzoylperoxytoluene, and benzoyl peroxide.
- peroxydicarbonate examples include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, Examples include di (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, and di (3-methyl-3-methoxybutylperoxy) dicarbonate.
- peroxyesters examples include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t -Hexylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis ( 2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl Hexanonate, t-butyl peroxyisobutyrate, 1,1-bis (t-butylperoxy) cycle Hexane
- peroxyketals examples include 1,1-bis (t-hexylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis ( t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, and 2,2-bis (t-butylperoxy) decane.
- dialkyl peroxide examples include ⁇ , ⁇ ′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t -Butylcumyl peroxide.
- hydroperoxide examples include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
- Examples of the azo compound include 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), and 2,2′-azobisisobutyronitrile. 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid) and 1,1′-azobis ( 1-cyclohexanecarbonitrile).
- Photoinitiators include, for example, benzoin ethers such as benzoin ethyl ether and isopropyl benzoin ether, benzyl ketals such as benzyl and hydroxycyclohexyl phenyl ketone, ketones and derivatives thereof such as benzophenone and acetophenone, thioxanthones, and bisimidazoles Are preferably used.
- photoinitiator When a photoinitiator is used, an appropriate photoinitiator is selected according to the wavelength of the light source to be used and the desired curing characteristics. If necessary, sensitizers such as amines, sulfur compounds and phosphorus compounds may be used in combination with the photoinitiator at an arbitrary ratio.
- Sensitizers include aliphatic amines, aromatic amines, cyclic amines such as piperidine having a nitrogen-containing cyclic structure, o-tolylthiourea, sodium diethyldithiophosphate, soluble sulfinic acid salts, N, N′-dimethyl -P-aminobenzonitrile, N, N'-diethyl-p-aminobenzonitrile, N, N'-di ( ⁇ -cyanoethyl) -p-aminobenzonitrile, N, N'-di ( ⁇ -chloroethyl)- P-aminobenzonitrile, tri-n-butylphosphine and the like are preferable.
- Sensitizers include propiophenone, acetophenone, xanthone, 4-methylacetophenone, benzophenone, fluorene, triphenylene, biphenyl, thioxanthone, anthraquinone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (Diethylamino) benzophenone, phenanthrene, naphthalene, 4-phenylacetophenone, 4-phenylbenzophenone, 1-iodonaphthalene, 2-iodonaphthalene, acenaphthene, 2-naphthonitrile, 1-naphthonitrile, chrysene, benzyl, fluoranthene, pyrene, 1, Non-pigment sensitizers such as 2-benzoanthracene, acridine, anthracene, perylene, tetracene and 2-methoxynaphthal
- free radical generators can be used singly or in combination of two or more. You may use combining a free radical generator, a decomposition accelerator, an inhibitor, etc.
- the content of the free radical generator is preferably 0.05% by weight to 10% by weight and more preferably 0.1% by weight to 5% by weight with respect to the entire adhesive component.
- the curing agent contains (c2) a latent curing agent from the viewpoint of obtaining a longer pot life.
- the latent curing agent includes, for example, an imidazole series, a hydrazide series, a boron trifluoride-amine complex, a sulfonium salt, an amine imide, and a polyamine. Or at least one selected from the group consisting of dicyandiamide.
- a latent curing agent may be combined with a decomposition accelerator, an inhibitor, and the like.
- the latent curing agent is preferably microencapsulated by coating with a polyurethane-based or polyester-based polymer substance because the pot life is extended.
- the dye preferably contains at least one dye selected from a black dye, a green dye, and a blue dye.
- the sensor using the most widely used red laser can be sufficiently recognized.
- the recognizability is higher than when the adhesive layer contains a blue dye which is a complementary color of red.
- a dye having a complementary color relationship with the color used for the laser and a dye having a complementary color relationship (a color located next to each color in the hue circle) It is preferable to use a dye having a color complementary to the color used in the laser.
- a red laser when used, a blue dye and / or a green dye is preferable, when a green / blue laser is used, a red dye is preferable, and when a red / yellow laser is used, a blue dye is preferable.
- the dye is preferably soluble in a low boiling point solvent such as toluene, methyl ethyl ketone or ethyl acetate from the viewpoint of suppressing aggregation during heating and pressurization.
- a low boiling point solvent such as toluene, methyl ethyl ketone or ethyl acetate
- the boiling point of the low boiling point solvent is preferably 50 to 140 ° C, more preferably 60 to 130 ° C. From the viewpoint of storage stability of the circuit connection material and connection reliability of the circuit connection structure, it is preferable to use a non-hydrophilic dye instead of a hydrophilic dye.
- the content of the dye is preferably 0.05 to 1.0 part by weight, more preferably 0.05 to 0.5 part by weight, and 0.05 to 0.3 part per 100 parts by weight of the adhesive component. Part by mass is more preferable. In this case, the visibility of the film-like circuit connecting material itself can be particularly improved, and after the film-like circuit connecting material is attached to the adherend, the alignment mark placed on the adherend is more easily recognized. be able to.
- FIG. 2 is a schematic cross-sectional view showing an embodiment of the conductive particles 5.
- the conductive particle 5 includes a core body 21 and a metal layer 22 that covers the surface of the core body 21.
- the core body 21 has a core portion 21a and a protrusion 21b formed on the surface of the core portion 21a.
- the metal layer 22 is formed so as to cover the entire core body 21 including the core portion 21a and the protruding portion 21b.
- the protrusion 14 is formed on the surface of the conductive particle 5 by the metal layer 22 that covers the protrusion 21 b.
- the core 21 is preferably a plastic core including an organic polymer compound such as plastic.
- a plastic core By using a plastic core, the cost of the core 21 can be reduced compared to a core made of metal.
- the plastic core is particularly suitable for circuit connection applications because it can secure an elastic deformation range with respect to a coefficient of thermal expansion and a dimensional change during pressure bonding.
- the organic polymer compound constituting the core 21a of the core 21 may be at least one selected from the group consisting of acrylic resin, styrene resin, benzoguanamine resin, silicone resin, polybutadiene resin, and copolymers thereof. Good. These may be cross-linked.
- the organic polymer compound that constitutes the protruding portion 21b of the core body 21 may be the same as or different from the organic polymer compound that constitutes the core portion 21a.
- the average particle size of the core 21a of the core 21 is preferably 2.0 ⁇ m to 3.5 ⁇ m, more preferably 2.0 ⁇ m to 3.25 ⁇ m, and 2.5 ⁇ m to 3.0 ⁇ m. Is more preferable.
- the average particle size is less than 1 ⁇ m, secondary aggregation of the particles occurs, and the insulation with an adjacent circuit tends to decrease.
- the average particle diameter exceeds 5 ⁇ m, the insulation from adjacent circuits tends to be reduced due to the size of the nucleus. Therefore, by making the average particle diameter of the core portion 21a within the above range, the insulation of the circuit can be more suitably secured.
- the core 21 can be formed, for example, by adsorbing a plurality of protrusions 21b having a smaller diameter than the core 21a on the surface of the core 21a.
- the core 21a and the protrusion 21b or both particles may be diluted with various coupling agents such as silane, aluminum, titanium, and an adhesive. After surface treatment, the method of mixing and adhering both is mentioned.
- the average particle size of the protrusions 21b is preferably 50 ⁇ m to 500 nm.
- the metal layer 22 preferably contains a metal having a Vickers hardness of 300 Hv or higher, such as Ni, Pd, Rh.
- Ni is included in the metal layer 22 as at least one selected from the group consisting of pure Ni, Ni alloy, and Ni oxide. Among these, pure Ni is preferable. Pure Pd is also preferred.
- the Ni alloy include Ni—B, Ni—W, Ni—B, Ni—W—Co, Ni—Fe, and Ni—Cr.
- Examples of the Ni oxide include NiO.
- the metal layer 22 may be composed of a single layer or may be composed of a plurality of layers.
- the outermost layer is a layer (metal plating) formed by plating containing at least one selected from the group consisting of Ni, Ni alloys, and Ni oxides. It is preferable.
- the Vickers hardness can be measured using, for example, “Maicroharadness Tester MHT-4 (trade name)” manufactured by Japan High-Tech, under the conditions of a load load of 20 kgf, a load speed of 20 kgf / second, and a holding time of 5 seconds.
- the metal layer 22 can be formed by, for example, plating the above metal on the core body 21 using an electroless plating method.
- the electroless plating method is roughly divided into a batch method and a continuous dropping method, and any method may be used.
- the thickness of the metal layer 22 is preferably 50 ⁇ m to 170 nm, more preferably 50 nm to 150 nm. By setting the thickness of the metal layer 22 in such a range, the connection resistance between the circuit electrodes can be reduced. If the thickness of the metal layer 22 is less than 50 nm, plating defects tend to occur, and if it exceeds 170 nm, condensation occurs between the conductive particles and a short circuit tends to occur between adjacent circuit electrodes. Therefore, by making the thickness of the metal layer 22 in the above range, the circuit electrodes can be more suitably connected.
- the nucleus 21 may be partially exposed.
- the coverage of the metal layer 22 with respect to the surface area of the core 21 is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. preferable.
- the height of the protrusion 14 of the conductive particle 5 is preferably 50 nm to 500 nm, and more preferably 75 nm to 300 nm. If the height of the protrusion 14 is less than 50 nm, the connection resistance tends to increase after the high temperature and high humidity treatment. When the height of the protrusion 14 exceeds 500 nm, the contact area between the conductive particles and the circuit electrode is reduced, and thus the connection resistance tends to increase. Therefore, the connection resistance can be more effectively suppressed by setting the height of the protruding portion 14 within the above range.
- the distance between adjacent protrusions 14 and 14 is preferably 1000 nm or less, and more preferably 500 nm or less. Moreover, the distance between the adjacent protrusions 14 and 14 is such that the cured body 11 (described later) of the adhesive component 3 does not enter between the conductive particles 5 and the circuit electrodes, and the conductive particles 5 and the circuit electrodes are sufficiently in contact with each other. Therefore, the thickness is preferably 50 nm or more. The height of the protrusion 14 and the distance between the adjacent protrusions 14 can be measured with an electron microscope.
- the conductive particles 5 may be configured such that the core body 21 is composed only of the core portion 21a without providing the protruding portion 21b.
- Such conductive particles 5 can be obtained by metal-plating the surface of the core portion 21a and forming the metal layer 22 having the protrusions 14 on the surface of the core portion 21a.
- Such protrusions 14 can be formed by partially changing the thickness of the metal layer 22 by changing the plating conditions during metal plating.
- a plating solution having a higher concentration than the plating solution used first can be added during the plating reaction to make the concentration of the plating solution non-uniform.
- the conductive particles 5 may be particles having a flat surface (simple sphere shape) without providing the protrusions 14.
- the conductive particles 5 as described above may be obtained by coating insulating particles such as non-conductive glass, ceramic, and plastic with a metal layer 22 containing Ni or the like.
- the metal layer 22 includes Ni and the core 21 is plastic, or when the conductive particles 5 are hot-melt metal particles, the metal particles 22 are deformable by heating and pressurization, and the conductive particles 5 and the circuit electrodes are connected at the time of connection. The contact area is increased and the connection reliability is improved, which is preferable.
- the content of the conductive particles 5 is preferably 0.1 to 20 parts by volume with respect to 100 parts by volume of the adhesive component 3 in the anisotropic conductive layer, and is appropriately adjusted depending on the application.
- the content of the conductive particles 5 is 0.1 volume parts to 10 volumes with respect to 100 volume parts of the adhesive component 3 in the anisotropic conductive layer from the viewpoint of more sufficiently suppressing short circuit between adjacent circuits. More preferably, it is a part.
- 10% compressive elasticity modulus of the conductive particles 5 (K value) is preferably 100kgf / mm 2 ⁇ 1000kgf / mm 2.
- the 10% compression modulus (K value) refers to the modulus of elasticity when the conductive particles 5 are 10% compressed and deformed, and can be measured by, for example, an H-100 microhardness meter manufactured by Fisher Instruments Inc.
- the average particle diameter of the conductive particles 5 is preferably 2.0 ⁇ m to 3.5 ⁇ m from the viewpoint of further easily suppressing a short circuit between adjacent circuit electrodes by making it lower than the height of the circuit electrodes to be connected.
- the thickness is more preferably 0.0 ⁇ m to 3.25 ⁇ m, and further preferably 2.5 ⁇ m to 3.0 ⁇ m.
- the “average particle diameter” of the conductive particles 5 means a particle diameter calculated without including the height of the protrusions 14.
- the average particle diameter of the conductive particles 5 can be measured as follows. First, 50 particles are arbitrarily selected from a particle image of conductive particles magnified 3000 times with a differential scanning electron microscope (SEM: for example, S800 manufactured by HITACHI). Next, using the enlarged particle image, for each of the selected plurality of particles, when there is a protrusion, the maximum diameter and the minimum diameter of the portion other than the protrusion are measured. The square root of the product of the maximum diameter and the minimum diameter of each particle is defined as the particle diameter of the particle. The particle diameter of each of 50 arbitrarily selected conductive particles is measured as described above, and the value obtained by dividing the sum of the particle diameters by the measured number of particles is taken as the average particle diameter.
- SEM differential scanning electron microscope
- the number of conductive particles 5 present per 1 mm 2 is preferably 2000 to 15000, and 3000 to 13000. More preferably. In that case, it is possible to obtain a contact area of the conductive particles sufficient to obtain a better connection resistance and to sufficiently prevent a short circuit between the circuits.
- the film-like circuit connecting material 1 of the present embodiment includes rubber fine particles, fillers, softeners, accelerators, anti-aging agents, colorants, flame retardants, thixotropic agents, coupling agents, phenol resins, melamines. You may contain resin, isocyanates, etc.
- the average particle size of the particles is not more than twice the average particle size of the conductive particles 5 to be blended, and the storage elastic modulus at room temperature (25 ° C.) is the room temperature of the conductive particles 5 and the adhesive component 3.
- the rubber fine particles are preferably at least one selected from the group consisting of silicone, acrylic emulsion, SBR, NBR, and polybutadiene rubber. These three-dimensionally crosslinked rubber fine particles have excellent solvent resistance and are easily dispersed in the adhesive component 3.
- the maximum diameter of the filler is preferably less than the average particle diameter of the conductive particles 5.
- the content of the filler is preferably in the range of 5% by volume to 60% by volume with respect to the entire circuit connecting adhesive film 1. When the content exceeds 60% by volume, the effect of improving reliability tends to be saturated.
- the coupling agent is preferably a compound containing one or more groups selected from the group consisting of a vinyl group, an acrylic group, an amino group, an epoxy group, and an isocyanate group, from the viewpoint of improving adhesiveness.
- the film-like circuit connecting material 1 melts and flows at the time of connection, and after the circuit electrodes facing each other are connected, it is cured to maintain the connection. Therefore, the fluidity of the circuit connecting material is an important factor.
- a film-like circuit connecting material 1 (adhesive layer 61) having a thickness of 35 ⁇ m and 5 mm ⁇ 5 mm is sandwiched between two glass plates having a thickness of 0.7 mm and 15 mm ⁇ 15 mm, under conditions of 170 ° C., 2 MPa, and 10 seconds.
- fluidity is evaluated by the value of (B) / (A) expressed using the initial area (A) and the area after heating and pressing (B). Can do.
- This (B) / (A) is preferably 1.3 to 3.0, and more preferably 1.5 to 2.5. If (B) / (A) is less than 1.3, the fluidity is insufficient and a good connection tends to be difficult to obtain. If it exceeds 3.0, bubbles are likely to be generated and the reliability is lowered.
- the elastic modulus at 40 ° C. after curing of the film-like circuit connecting material 1 is preferably 100 MPa to 3000 MPa, and more preferably 500 MPa to 2000 MPa.
- FIG. 3 is a schematic cross-sectional view showing an embodiment of a circuit connection structure.
- the circuit connection structure 100 includes a circuit member (first circuit member) 30 and a circuit member (second circuit member) 40 facing each other, and the circuit member 30 and the circuit member 40. And a circuit connecting member 10 for connecting them.
- the circuit member 30 includes a circuit board 31 and a circuit electrode (first circuit electrode) 32 formed on the main surface 31 a of the circuit board 31.
- the circuit member 40 includes a circuit board 41 and a circuit electrode (second circuit electrode) 42 formed on the main surface 41 a of the circuit board 41.
- the material of the circuit boards 31 and 41 is not particularly limited, but is usually an organic insulating material, glass or silicon.
- Examples of the material of the circuit electrodes 32 and 42 include Au, Ag, Sn, and Pt group metals, indium-tin oxide (ITO), indium-zinc oxide (IZO), Al, and Cr.
- At least one of the circuit electrodes 32 and 42 preferably contains at least one of indium-tin oxide (ITO) and indium-zinc oxide (IZO) from the viewpoint of significantly improving electrical connection.
- the circuit electrodes 32 and 42 may be entirely made of the above material, or only the outermost layer may be made of the above material.
- At least one of the circuit members 30 and 40 preferably a circuit member that is a flexible substrate, has a circuit pitch (interval between circuit electrodes) of 200 ⁇ m or less.
- the lower limit of the circuit pitch is not particularly limited, but may be about 20 ⁇ m, for example.
- the surfaces of the circuit electrodes 32 and 42 are preferably flat.
- “the surface of the circuit electrode is flat” means that the unevenness of the surface of the circuit electrode is 20 nm or less.
- the conductive film 5 is pressed when the circuit connecting adhesive film 1 is pressed between the circuit member 30 and the circuit member 40.
- the protruding portion of the particle 5 penetrates the circuit electrodes 32 and 42 and directly contacts the circuit boards 31 and 41. Therefore, by setting the thickness of the circuit electrodes 32 and 42 to 50 nm or more, the contact area between the circuit electrodes 32 and 42 and the conductive particles 5 can be increased, and the connection resistance can be further reduced.
- the thickness of the circuit electrodes 32 and 42 is preferably 1000 nm or less, and more preferably 500 nm or less, from the viewpoint of manufacturing cost.
- an insulating layer may be further provided between the circuit electrode 32 and the circuit board 31.
- an insulating layer may be further provided between the circuit electrode 42 and the circuit board 41.
- the material of the insulating layer is not particularly limited as long as it is made of an insulating material, but is usually an organic insulating material, silicon dioxide or silicon nitride.
- first circuit member 30 and the second circuit member 40 include chip parts such as semiconductor chips, resistor chips, capacitor chips, and substrates such as printed boards. These circuit members 30 and 40 are usually provided with a large number of circuit electrodes (connection terminals) 32 and 42 (in some cases, the number may be one).
- the circuit connection member 10 is a layer formed by curing the above-described film-like circuit connection material 1.
- the circuit connection member 10 includes a cured body 11 formed by curing the adhesive component 3 and the conductive particles 5.
- the facing circuit electrode 32 and the circuit electrode 42 are electrically connected via the conductive particles 5. That is, the circuit electrodes are electrically connected by the conductive particles 5 being in direct contact with both the circuit electrodes 32 and 42.
- the conductive particles 5 have a plurality of protrusions, it is preferable that a part of the protrusions bite into the circuit electrode 32 or the circuit electrode 42. In this case, the contact area between the protrusions of the conductive particles and the circuit electrodes 32 and 42 can be further increased, and the connection resistance can be further reduced.
- FIG. 4 is a process diagram schematically showing a method for manufacturing a circuit connection structure.
- FIG. 4A shows a state before the circuit members are connected to each other
- FIG. 4B shows a state when the circuit members are connected to each other
- FIG. The circuit connection structure after connecting is shown.
- an LCD panel 73 having a circuit electrode 72 and a liquid crystal display 74 on the main surface is prepared.
- a film-like circuit connecting material (adhesive layer) 61 equivalent to the film-like circuit connecting material 1 is adhered and placed on the circuit electrode 72.
- the circuit board 75 provided with the circuit electrode 76 such as COF is aligned so that the circuit electrode 72 and the circuit electrode 76 face each other through the film-like circuit connecting material 61.
- the circuit electrode 72 and the circuit electrode 76 have, for example, a structure in which a plurality of electrodes are arranged.
- the circuit electrode 72 and the circuit electrode 76 are opposed to each other through the film-like circuit connecting material 61 while aligning the LCD panel 73 and the circuit board 75. Then, the circuit board 75 is placed on the film-like circuit connecting material 61. Thereby, the circuit electrode 72 and the circuit electrode 76 can be connected by the conductive particles 5 in the film-like circuit connecting material 61.
- the circuit board 75 is pressurized from the surface opposite to the surface on which the circuit electrode 76 is disposed (in the direction of arrow A in FIG. 4B), and the film-like circuit connecting material 61 is heated. Thereby, the film-form circuit connection material 61 hardens
- the method for the curing treatment one or both of heating and light irradiation can be employed depending on the adhesive component used.
- Example 1 400 parts by mass of polycaprolactone diol having a weight average molecular weight of 800, 131 parts by mass of 2-hydroxypropyl acrylate, 0.5 parts by mass of dibutyltin dilaurate as a catalyst, and 1.0 part by mass of hydroquinone monomethyl ether as a polymerization inhibitor, The mixture was heated to 50 ° C. with stirring. Next, 222 parts by mass of isophorone diisocyanate was added dropwise, and the mixture was further heated to 80 ° C. with stirring to conduct a urethanization reaction. After confirming that the reaction rate of the isocyanate group was 99% or more, the reaction temperature was lowered to obtain urethane acrylate.
- the dicarboxylic acid was terephthalic acid
- the diol was propylene glycol
- the isocyanate was 4,4'-diphenylmethane diisocyanate
- the molar ratio of terephthalic acid / propylene glycol / 4,4'-diphenylmethane diisocyanate was 1.0 / 1.3 / 0. 25 polyester urethane resins A were prepared.
- polyester urethane resin A was dissolved in methyl ethyl ketone to obtain a solution having a concentration of 20% by mass.
- the methyl ethyl ketone solution of the polyester urethane resin A was applied to a PET film having a thickness of 80 ⁇ m, one side of which was surface-treated (silicone treatment), using a coating apparatus. Furthermore, a film having a thickness of 35 ⁇ m was formed by hot air drying at 70 ° C. for 10 minutes.
- 25 parts by mass of the urethane acrylate as a radical polymerizable substance 20 parts by mass of isocyanurate type acrylate (product name: M-325, manufactured by Toagosei Co., Ltd.), 2-methacryloyloxyethyl acid phosphate (product name: P-2M 1 part by mass of Kyoeisha Chemical Co., Ltd.) and 4 parts by mass of benzoyl peroxide (product name: Nyper BMT-K40, manufactured by NOF Corporation) as a free radical generator are used as a film-forming polymer (thermoplastic resin).
- isocyanurate type acrylate product name: M-325, manufactured by Toagosei Co., Ltd.
- 2-methacryloyloxyethyl acid phosphate product name: P-2M 1 part by mass of Kyoeisha Chemical Co., Ltd.
- benzoyl peroxide product name: Nyper BMT-K40, manufactured by NOF Corporation
- the polyester urethane resin A was mixed with 55 parts by mass of a 20% by mass methyl ethyl ketone solution, and further 0.5 parts by mass of a black dye (product name: NUbian BLACK, manufactured by Orient Kogyo Co., Ltd.) was dispersed and stirred as an adhesive component.
- a binder resin solution was obtained.
- the conductive particles (average particle diameter: 3 ⁇ m, hereinafter referred to as “inner particle size: 3 ⁇ m”, which has polystyrene particles as cores and outermost layers containing Ni and covering the cores, and having protrusions formed on the surface of the outermost layer. "Ni-coated particles”) were prepared.
- the conductive particles are blended in a ratio of 2 % by volume (particle number: 7000 particles / mm 2 ) based on the volume of the adhesive component with respect to the solution of the adhesive component, and include the adhesive component (binder resin). Dispersed in the solution.
- the obtained liquid mixture was apply
- An adhesive layer (width 15 cm, length 70 m) having a thickness of 18 ⁇ m was formed as the anisotropic conductive adhesive layer A by hot air drying at 70 ° C. for 10 minutes.
- the anisotropic conductive adhesive layer A thus obtained was cut to a width of 1.5 mm, and wound on a plastic reel with the adhesive film surface (adhesive layer surface) inside for 50 m to obtain a tape-like film-like circuit connection material. .
- Examples 2 to 16 In the same manner as in Example 1, except that the average particle diameter of conductive particles, the number of conductive particles, the type of dye, the amount of dye, and the thickness of the film-like circuit connection material were changed as shown in FIG. The material was made.
- Examples 17 and 18 25 parts by mass of the urethane acrylate as a radical polymerizable substance, 20 parts by mass of isocyanurate type acrylate (product name: M-325, manufactured by Toagosei Co., Ltd.), 2-methacryloyloxyethyl acid phosphate (product name: P-2M ) 1 part by mass and 4 parts by mass of benzoyl peroxide (product name: Nyper BMT-K40) as a free radical generator are added to 55 parts by mass of a 20% by mass methyl ethyl ketone solution of polyester urethane resin A as a film-forming polymer. Further, 0.5 parts by mass of a black dye (product name: NUBIAN BLACK, manufactured by Orient Kogyo Co., Ltd.) was dispersed and stirred to obtain a solution of a binder resin as an adhesive component.
- a black dye product name: NUBIAN BLACK, manufactured by Orient Kogyo Co., Ltd.
- conductive particles (average particle size: 3 ⁇ m) having polystyrene particles as a core and an outermost layer containing Ni that covers the core and having protrusions formed on the surface of the outermost layer were prepared.
- 4% by volume (6000 / mm 2 ) of the conductive particles were mixed with the binder resin solution based on the volume of the adhesive component, and dispersed in the binder resin.
- the obtained liquid mixture was apply
- the obtained adhesive component solution was applied to the side of the PET film having a thickness of 50 ⁇ m having one surface treated (silicone treatment) on which the surface treatment was not performed using a coating apparatus.
- An adhesive layer B (width 15 cm, length 70 m) having a thickness of 10 ⁇ m was formed by hot air drying at 70 ° C. for 10 minutes.
- the anisotropic conductive adhesive layer A and the adhesive layer B were superposed and laminated using a laminator (RISTON manufactured by Dupont, model; HRL, roll pressure was spring load only, roll temperature 40 ° C., speed 50 cm / min). Thereafter, the PET film on the anisotropic conductive adhesive layer A side was peeled off to obtain a two-layer adhesive layer (width 15 cm, length 60 m) having a thickness of 14 ⁇ m as an anisotropic conductive adhesive.
- the obtained anisotropic conductive adhesive was cut to a width of 1.5 mm, and wound on a plastic reel with an adhesive film surface inside by 50 m to obtain a tape-like film-like circuit connecting material.
- Example 1 except that the average particle size of the conductive particles, the number of particles of the conductive particles, the thickness of the film-like circuit connecting material, the dye amount, and the layer configuration of the film-like circuit connecting material were changed as shown in FIG. Thus, a film-like circuit connecting material was produced.
- circuit connection The adhesive layer of the film-like circuit connecting material (width 1.5 mm, length 3 cm) obtained in the examples and comparative examples was heated and pressed at 70 ° C. and 1 MPa for 1 second to have a thickness of 0.7 mm. Transferred onto a Cr / indium-zinc oxide (IZO) coated glass substrate. After the transfer, the PET film was peeled off. Next, a flexible circuit board (FPC) having 500 tin-plated copper circuits with a pitch of 40 ⁇ m and a thickness of 8 ⁇ m was placed on the transferred adhesive layer, and temporarily fixed by pressing at 24 ° C. and 0.5 MPa for 1 second.
- FPC flexible circuit board
- a flexible circuit board having 100 copper circuits (pitch 100 ⁇ m, thickness 18 ⁇ m) plated with gold was used.
- the temporarily fixed glass substrate was installed in the main pressure bonding apparatus, and heated and pressed at 180 ° C. and 3 MPa for 5 seconds from the FPC side with a heat tool while using a 150 ⁇ m-thick Teflon (registered trademark) sheet as a cushioning material.
- the FPC and the glass substrate were connected over a width of 1.5 mm to obtain a connection body.
- connection resistance About the said connection body, the resistance value in each electrode was measured with the digital multimeter (device name: TR6845, product made from an Advantest company) by 4 terminal method, and the average value of 10 electrodes was calculated
- FIG. 7 is a diagram showing the evaluation results of the film for circuit connection according to the example and the comparative example. It can be seen from Reference Example 1 that when conductive particles having an average particle diameter larger than 3.5 ⁇ m are used, the problem of visibility does not occur.
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Abstract
Description
使用機器:日立L-6000型((株)日立製作所製、商品名)
検出器:L-3300RI((株)日立製作所製、商品名)
カラム:ゲルパックGL-R420+ゲルパックGL-R430+ゲルパックGL-R440(計3本)(日立化成工業(株)製、商品名)溶離液:テトラヒドロフラン
測定温度:40℃
流量:1.75ml/min
重量平均分子量800のポリカプロラクトンジオール400質量部と、2-ヒドロキシプロピルアクリレート131質量部と、触媒としてジブチル錫ジラウレート0.5質量部と、重合禁止剤としてハイドロキノンモノメチルエーテル1.0質量部とを、攪拌しながら50℃に加熱して混合した。次いで、イソホロンジイソシアネート222質量部を滴下し、更に攪拌しながら80℃に昇温してウレタン化反応を行った。イソシアネート基の反応率が99%以上になったことを確認後、反応温度を下げてウレタンアクリレートを得た。
導電粒子の平均粒子径、導電粒子個数、染料種、染料量、フィルム状回路接続材料の厚みを、図5に示すように変化させた以外は、実施例1と同様にして、フィルム状回路接続材料を作製した。
ラジカル重合性物質としての上記ウレタンアクリレート25質量部、イソシアヌレート型アクリレート(製品名:M-325、東亞合成社製)20質量部、2-メタクリロイロキシエチルアッシドホスフェート(製品名:P-2M)1質量部、及び遊離ラジカル発生剤としてのベンゾイルパーオキサイド(製品名:ナイパーBMT-K40)4質量部を、フィルム形成性高分子としてのポリエステルウレタン樹脂Aの20質量%メチルエチルケトン溶液55質量部に混合し、更に黒色染料(製品名:NUBIAN BLACK、オリエント工業社製)を0.5質量部分散させ、攪拌して、接着剤成分としてのバインダ樹脂の溶液を得た。
導電粒子の平均粒径、導電粒子の粒子数、フィルム状回路接続材料の厚み、染料量、フィルム状回路接続材料の層構成を図6に示すように変化させた以外は、実施例1と同様にして、フィルム状回路接続材料を作製した。
実施例、比較例で得られたフィルム状回路接続材料(幅1.5mm、長さ3cm)の接着剤層を、70℃、1MPaで1秒間の加熱及び加圧により、厚さ0.7mmのCr/インジウム-亜鉛酸化物(IZO)コートガラス基板上に転写した。転写後、PETフィルムを剥離した。次いで、ピッチ40μm、厚さ8μmのすずめっき銅回路を500本有するフレキシブル回路板(FPC)を、転写した接着剤層上に置き、24℃、0.5MPaで1秒間加圧して仮固定した。(但し、導電粒子の径が10μmのサンプルについては、金でめっきされた銅回路(ピッチ100μm、厚さ18μm)を100本有するフレキシブル回路基板を用いた。FPCが回路接続材料の接着剤層によって仮固定されたガラス基板を本圧着装置に設置した。150μm厚さのテフロン(登録商標)シートをクッション材として用いながら、FPC側から、ヒートツールによって180℃、3MPaで5秒間加熱及び加圧して、FPCとガラス基板とを幅1.5mmにわたり接続し、接続体を得た。
上記接続体について、4端子法によりそれぞれの電極における抵抗値をデジタルマルチメータ(装置名:TR6845、アドバンテスト社製)で測定し、10本の電極の平均値を求めた。
オリンパス(株)製BH3-MJL液晶パネル検査用顕微鏡を用い、フィルム状回路接続材料をその厚み方向から観察し、1mm2当たりの導電粒子の個数を画像解析により測定した。
フィルム状回路接続材料(幅1.5mm、長さ3cm)の接着剤層を、70℃、1MPaで1秒間加熱及び加圧することにより、厚さ0.7mmのスライドガラス基板上に転写し、PETフィルムを剥離して、試料を準備した。白色の作業台にA4サイズのOA用紙を置き、その上に前記試料を乗せた。KEYENCE社製Switching Power Supply MS2-H50に赤色LED光源としてハイブリッドファイバセンサFS-V11を搭載したセンサを用いて、フィルム状回路接続材料が貼り付けられた部分(B)と貼り付けられていないスライドガラスのみの部分(A)に対して、フィルム状回路接続材料側から赤色光を照射し、それぞれの部分における反射光の強度を測定した。部分(A)と部分(B)との反射光の強度の値の差が十分大きい場合をOK、小さい場合をNGと判定した。
フィルム状回路接続材料(幅1.2mm、長さ4cm)の接着剤層を、Panasonic社製フィルム状回路接続材料貼り付け装置を用いて、70℃、1MPaで1秒間加熱及び加圧することにより、厚さ0.7mmのTFTガラス基板上に転写し、PETフィルムを剥離した。そして、同装置に設置されたレーザーセンサを用い、ガラス基板上にフィルム状回路接続材料が適性に貼り付けられているかどうかをフィルム側から確認した。いずれのフィルム回路状接続材料に関しても、フィルム側からの視認性に問題はなかった。
フィルム状回路接続材料(幅1.5mm、長さ3cm)の接着剤層を70℃、1MPaで1秒間加熱及び加圧して、位置あわせマークが搭載された、すずでめっきされた銅回路(ピッチ40μm、厚さ6μm)を500本有するフレキシブル回路板(FPC)上に転写し、PETフィルムを剥離して、試料を準備した。前記試料をオリンパス(株)製BH3-MJL液晶パネル検査用顕微鏡を用いてフィルム状回路接続材料の厚み方向から観察し、位置あわせマーク部が視認可能であるか否かを確認した。位置あわせマークの視認が可能である場合をA、位置合わせマークの確認が比較的困難なことがあった場合をB、位置あわせマークの視認ができなかった場合をCと判定した。
Claims (3)
- 対向する回路電極間に介在して前記回路電極同士を電気的に接続するために用いられる接着剤層を有し、
前記接着剤層が、
(a)熱可塑性樹脂、(b)硬化性物質、(c)硬化剤、及び(d)染料を含有する接着剤成分と、
プラスチック核体及び該プラスチック核体を被覆する金属層を有し、該金属層の最外層が、Ni、Ni合金及びNi酸化物からなる群より選ばれる少なくとも1種を含む、めっきにより形成された層であり、平均粒径が2.0~3.5μmである導電粒子と、
を含む、フィルム状回路接続材料。 - 前記導電粒子の個数が、前記接着剤層の厚み方向から見たときに2000~15000個/mm2である、請求項1に記載のフィルム状回路接続材料。
- 第1の回路電極を有する第1の回路部材と、第2の回路電極を有する第2の回路部材との間に請求項1又は2に記載のフィルム状回路接続材料の接着剤層を介在させながら、前記フィルム状回路接続材料を加熱及び加圧することによって前記第1の回路電極及び前記第2の回路電極を電気的に接続して得られる、回路接続構造体。
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WO2015108025A1 (ja) * | 2014-01-16 | 2015-07-23 | デクセリアルズ株式会社 | 接続体、接続体の製造方法、接続方法、異方性導電接着剤 |
JP2020053403A (ja) * | 2014-03-31 | 2020-04-02 | デクセリアルズ株式会社 | 異方性導電フィルム及びその製造方法 |
CN114479712A (zh) * | 2017-04-28 | 2022-05-13 | 昭和电工材料株式会社 | 粘接剂组合物及连接体的制造方法 |
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JP6508677B2 (ja) * | 2015-03-20 | 2019-05-08 | デクセリアルズ株式会社 | 異方性導電接続方法及び異方性導電接続構造体 |
KR102542827B1 (ko) * | 2015-11-11 | 2023-06-14 | 세키스이가가쿠 고교가부시키가이샤 | 입자, 입자 재료, 접속 재료 및 접속 구조체 |
WO2017104665A1 (ja) * | 2015-12-15 | 2017-06-22 | 積水化学工業株式会社 | 導電性粘着テープ |
CN110300780A (zh) * | 2017-03-06 | 2019-10-01 | 迪睿合株式会社 | 树脂组合物、树脂组合物的制备方法和结构体 |
WO2018181546A1 (ja) * | 2017-03-29 | 2018-10-04 | 日立化成株式会社 | 導電粒子の選別方法、回路接続材料、接続構造体及びその製造方法、並びに導電粒子 |
KR20210141953A (ko) * | 2019-03-13 | 2021-11-23 | 쇼와덴코머티리얼즈가부시끼가이샤 | 회로 접속용 접착제 필름 및 그 제조 방법, 회로 접속 구조체의 제조 방법, 및, 접착제 필름 수용 세트 |
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JPH11293133A (ja) * | 1998-04-14 | 1999-10-26 | Nippon Zeon Co Ltd | 樹脂組成物 |
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WO2015108025A1 (ja) * | 2014-01-16 | 2015-07-23 | デクセリアルズ株式会社 | 接続体、接続体の製造方法、接続方法、異方性導電接着剤 |
JP2020053403A (ja) * | 2014-03-31 | 2020-04-02 | デクセリアルズ株式会社 | 異方性導電フィルム及びその製造方法 |
JP7017158B2 (ja) | 2014-03-31 | 2022-02-08 | デクセリアルズ株式会社 | 異方性導電フィルム及びその製造方法 |
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CN114479712A (zh) * | 2017-04-28 | 2022-05-13 | 昭和电工材料株式会社 | 粘接剂组合物及连接体的制造方法 |
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