WO2010038753A1 - 異方性導電接着剤及びそれを用いた接続構造体の製造方法 - Google Patents
異方性導電接着剤及びそれを用いた接続構造体の製造方法 Download PDFInfo
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- WO2010038753A1 WO2010038753A1 PCT/JP2009/066987 JP2009066987W WO2010038753A1 WO 2010038753 A1 WO2010038753 A1 WO 2010038753A1 JP 2009066987 W JP2009066987 W JP 2009066987W WO 2010038753 A1 WO2010038753 A1 WO 2010038753A1
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- anisotropic conductive
- conductive adhesive
- flexible printed
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C09J11/08—Macromolecular 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
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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
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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
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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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
- 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
- C09J2409/00—Presence of diene rubber
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- H05K3/36—Assembling printed circuits with other printed circuits
- H05K3/361—Assembling flexible printed circuits with other printed circuits
Definitions
- the present invention relates to an anisotropic conductive adhesive in which conductive particles are dispersed in an insulating adhesive component, and a method for manufacturing a connection structure using the same.
- an anisotropic conductive adhesive is used for the terminal electrode of the glass substrate and the terminal electrode of the flexible printed circuit board. Both terminal electrodes are electrically connected by pressing the terminal electrodes while heating and curing the anisotropic conductive adhesive using a heating tool (Patent Document 1).
- the linear expansion coefficient (10 to 40 ⁇ 10 ⁇ 6 / ° C.) of a polyimide resin generally used as a base material of a flexible printed wiring board is equal to the linear expansion coefficient of glass (about 8.5 ⁇ 10 ⁇ 6 / ° C.).
- the flexible printed wiring board expands and contracts (expands) more than the glass substrate due to the heat of the heating tool during FOG bonding. When the terminal electrode pitch is reduced, sufficient electrical connection tends to be difficult.
- the design interval of the terminal electrode of the flexible printed wiring board is formed at an interval narrower than the design interval of the terminal electrode of the corresponding glass substrate (sometimes referred to as a predetermined interval), and the anisotropic conductive adhesive It has been practiced in the field to extend the distance from the heating tool at the time of heat-curing to a predetermined interval to suppress the dimensional deviation between the terminal electrodes of the glass substrate and the flexible wiring board.
- the operating conditions of the heating tool during FOG bonding may vary slightly for each FOG bonding, or manufacturing requirements If the operating condition of the heating tool is slightly changed, there is a case where good electrical connection with the anisotropic conductive adhesive cannot be achieved.
- the anisotropic conductive adhesive is prevented from being cured before the terminals on the printed wiring board reach the terminals of the glass substrate, thereby both terminals of the glass substrate and the flexible printed circuit board.
- the heating tool is brought into contact with and pressed against the flexible printed wiring board at a relatively high speed, but the terminal electrode of the flexible printed wiring board is narrowed. There is a concern that it is not possible to ensure a sufficient time for extending the interval formed in this way to the terminal electrode interval of the glass substrate.
- An object of the present invention is to solve the above conventional problems, and an anisotropic conductive adhesive capable of realizing high electrical connection reliability even when a heating tool is contacted and pressed at a low speed. It is to provide a method of manufacturing a connection structure using the same.
- the curing component of the anisotropic conductive adhesive is mainly composed of a radical polymerizable compound, while the minimum melt viscosity is in the range of 100 to 800 Pa ⁇ s, and the minimum melt viscosity is It has been found that by setting the temperature reaching 90 to a very narrow range of 90 to 115 ° C., a good anisotropic conductive connection can be realized even if the speed of the heating tool is reduced, and the present invention has been completed.
- the present invention is an anisotropic conductive adhesive in which conductive particles are dispersed in an insulating adhesive component containing a radical polymerizable compound, a radical initiator, and a film-forming resin.
- an anisotropic conductive adhesive characterized in that the minimum melt viscosity is in the range of 100 to 800 Pa ⁇ s, and the temperature showing the minimum melt viscosity is in the range of 90 to 115 ° C.
- the present invention connects a glass substrate on which terminal electrodes are formed at a predetermined interval and a flexible printed wiring board on which terminal electrodes are formed at an interval narrower than the predetermined interval using an anisotropic conductive adhesive.
- steps (A) and (B) (A) An arrangement step of arranging the anisotropic conductive adhesive of the present invention between the terminal electrode of the glass substrate and the terminal electrode of the flexible printed wiring board; and (B) the flexible printed wiring board side.
- the manufacturing method is characterized by having a connecting step of pressing the heating tool and heating and pressing at a temperature equal to or higher than the minimum melt viscosity to electrically connect the terminal electrodes.
- the anisotropic conductive adhesive of the present invention has the characteristics that its minimum melt viscosity is 100 to 800 Pa ⁇ s and the temperature indicating the minimum viscosity range is 90 to 115 ° C. For this reason, the glass substrate on which the terminal electrodes are formed at predetermined intervals and the flexible printed wiring board on which the terminal electrodes are formed at intervals smaller than the predetermined intervals are connected using the anisotropic conductive adhesive of the present invention. When trying to do so, high fluidity can be secured even in a state of being sandwiched between the glass substrate and the flexible printed wiring board while sufficiently expanding the terminal electrode interval of the flexible printed wiring board. As a result, it is possible to provide a connection structure having high connection reliability even when the pressing speed of the heating tool varies somewhat in production or at a low speed.
- FIG. 1A is an explanatory diagram of a method for joining a glass substrate and a flexible printed wiring board.
- FIG. 1B is an explanatory diagram of a method for joining the glass substrate and the flexible printed wiring board following FIG. 1A.
- the anisotropic conductive adhesive of the present invention is obtained by dispersing conductive particles in an insulating adhesive component containing a radical polymerizable compound, a radical initiator, and a film-forming resin.
- the minimum melt viscosity is in the range of 100 to 800 Pa ⁇ s, preferably 100 to 400 Pa ⁇ s, and the temperature showing the minimum melt temperature is 90 to 115 ° C, preferably 95 to 110 ° C.
- the minimum melt viscosity is 100 to 800 Pa ⁇ s, if it is 100 Pa ⁇ s or more, excessive flow when the anisotropic conductive adhesive is heated and pressed can be avoided. This is because a necessary amount of adhesive can be secured between the electrodes. If the minimum melt viscosity exceeds 800 Pa ⁇ s, the fluidity of the anisotropic conductive adhesive during heat pressing decreases, and the connection thickness becomes larger than the diameter of the conductive particles. This is because of a decrease.
- an anisotropic conductive adhesive having a minimum melting temperature lower than 90 ° C. quickly reaches a region where the melt viscosity is increased based on the subsequent heating and pressurizes, and the fluidity rapidly decreases.
- the curing of most of the anisotropic conductive adhesive proceeds before the intervals are sufficiently expanded, and both the glass substrate and the flexible printed wiring board are used. This is because the contact between the terminal electrode and the conductive particles becomes insufficient.
- the anisotropic conductive adhesive having a minimum melt viscosity exceeding 115 ° C. ends the predetermined time of heating and pressing by the heating tool without sufficiently performing the curing reaction itself. This is because the contact between the terminal electrodes on both the glass substrate and the flexible printed wiring board and the conductive particles becomes insufficient.
- the optimum range of the minimum melt viscosity is 100 to 800 Pa ⁇ s, and the optimum range of the temperature showing the minimum melt viscosity is 90 to 115 ° C. Therefore, the minimum melt viscosity is the minimum melt viscosity.
- the optimum range of the value [(minimum melt viscosity) / (temperature exhibiting the minimum melt viscosity)] divided by the temperature indicating is 0.88 to 8.8.
- the conductive particles of the anisotropic conductive adhesive of the present invention are, for example, metal particles such as nickel, gold and copper, those obtained by applying gold plating to resin particles, and the outermost layer of particles obtained by applying gold plating to resin particles Those having an insulating coating applied thereto can be used.
- the average particle diameter of the conductive particles is preferably 1 to 20 ⁇ m, more preferably 2 to 10 ⁇ m, from the viewpoint of conduction reliability.
- the content of the conductive particles in the insulating adhesive component is preferably 2 to 50% by mass, more preferably 3 to 20% by mass, from the viewpoint of conduction reliability and insulation reliability.
- the insulating adhesive component contains at least a radical polymerizable compound, a radical polymerization initiator, and a film-forming resin.
- Radical polymerizable compounds include (meth) acrylate monomers such as dicyclopentanyl (meth) acrylate and phosphorus-containing (meth) acrylate, and (meth) acrylate oligomers such as urethane (meth) acrylate and polyester (meth) acrylate Can be used. Especially, it is preferable at least one of a dicyclopentanyl (meth) acryl monomer and a urethane (meth) acrylate oligomer from the point which can make melt viscosity and a cure rate compatible preferably. In addition, other radically polymerizable compounds capable of radical polymerization with these monomers and oligomers can be used in combination as long as the effects of the present invention are not impaired.
- radical initiator a known radical polymerization initiator can be used, and among them, a peroxide radical initiator can be preferably used.
- peroxide radical initiator include diacyl peroxides such as benzoyl peroxide, alkyl peresters such as t-hexyl peroxypivalate and t-butyl peroxybenzoate, and 1,1-di ( Preferred examples include peroxyketals such as (t-butylperoxy) cyclohexane.
- Nyper BW diacyl peroxide, NOF Corporation
- NIPPER BMT-K40 diacyl peroxide, NOF Corporation
- NIPA BO diacyl peroxide, NOF Corporation
- Nyper FF Diacyl peroxide, NOF Corporation
- NIPER BS diacyl peroxide, NOF Corporation
- NIPER E diacyl peroxide, NOF Corporation
- NIPER NS diacyl peroxide, NOF Corporation
- perhexyl O peroxyester, NOF Corporation
- perbutyl O peroxyester, NOF Corporation
- the film-forming resin provides an insulating adhesive component containing a radically polymerizable compound and an anisotropic conductive adhesive comprising the insulating adhesive component, thereby facilitating film formation, and the anisotropic conductive adhesive. It increases the overall cohesive strength.
- the film-forming resin in particular, at least one of a phenoxy resin or a mixed resin of a phenoxy resin and an epoxy resin generated in the production process of the phenoxy resin can be preferably used.
- the weight average molecular weight of the phenoxy resin or mixed resin is preferably 20,000 to 60,000, more preferably 20,000 to 40,000 in consideration of the film strength and fluidity of the anisotropic conductive adhesive. This is because if the weight average molecular weight is 20000 or more, excessive flow when the anisotropic conductive adhesive is heated can be avoided, and if it is 60000 or less, insufficient fluidity does not occur.
- the insulating adhesive component preferably contains a stress relaxation agent.
- a stress relaxation agent By including a stress relaxation agent, it is possible to reduce the strength of internal stress generated at the interface portion between the anisotropic conductive adhesive and the glass substrate and at the interface portion between the anisotropic conductive adhesive and the flexible printed wiring board. .
- a rubber-based elastic material can be preferably used, and is preferably used in a particle shape.
- the rubber-based elastic material include butadiene rubber (BR), acrylic rubber (ACR), and nitrile rubber (NBR) made of polybutadiene.
- BR butadiene rubber
- ACR acrylic rubber
- NBR nitrile rubber
- butadiene rubber (BR) made of polybutadiene is preferable because it has high resilience compared to acrylic rubber (ACR), nitrile rubber (NBR), and the like, and can absorb a lot of internal stress. Therefore, in the present invention, it is particularly preferable to use polybutadiene particles as the stress relaxation agent.
- the polybutadiene particles used in the present invention it is preferable to use particles having an elastic modulus smaller than that of the anisotropic conductive adhesive after curing. Since there is a tendency that the internal stress of a cured product of the isotropic conductive adhesive cannot be made sufficiently small, one having an elastic modulus of 1 ⁇ 10 8 to 1 ⁇ 10 10 dyn / cm 2 is preferably used.
- the average particle size is the average particle size of the conductive particles. It is preferable to be smaller, but if it is too small, the internal stress cannot be absorbed, and if it is too large, there is a concern that sufficient electrical connection between the conductive particles and the connection electrode cannot be obtained. Preferably, one having a thickness of 0.01 to 0.5 ⁇ m is used.
- the content ratio of the polybutadiene particles as described above in the anisotropic conductive adhesive is preferably 10 to 30 parts by mass, more preferably 15 to 15 parts by mass with respect to 75 parts by mass in total of the radical polymerizable compound and the film-forming resin. 25 parts by mass. If the content ratio is 10 parts by mass or more, the internal stress generated in the anisotropic conductive adhesive can be sufficiently reduced, and if it is 30 parts by mass or less, the anisotropic conductive adhesive is adversely affected. It is possible to prevent the heat resistance from being deteriorated.
- a radically polymerizable compound and a film-forming resin are dissolved in a solvent, then a predetermined amount of radical initiator and conductive particles are added, and a stress relaxation agent (preferably polybutadiene particles) is added and mixed as necessary. Stir.
- This mixed solution is coated on a release film such as a polyester film, and after drying, a cover film is laminated to obtain a filmed anisotropic conductive adhesive.
- the anisotropic conductive adhesive of the present invention described above can be preferably used when manufacturing a connection structure by anisotropically connecting a glass substrate such as a liquid crystal panel and a flexible printed wiring board.
- a method for manufacturing such a connection structure will be described below with reference to FIGS. 1A and 1B (an explanatory diagram of a method for joining a glass substrate and a flexible printed wiring board).
- an anisotropic conductive adhesive includes a glass substrate on which terminal electrodes are formed at predetermined intervals and a flexible printed wiring board on which terminal electrodes are formed at intervals smaller than the predetermined intervals. It is a manufacturing method of the connection structure formed by using, and is a method having the following steps (A) and (B).
- the previously described anisotropic conductive adhesive of the present invention is disposed between the terminal electrode of the glass substrate and the terminal electrode of the flexible printed wiring board.
- a conventionally known method can be used except that the anisotropic conductive adhesive of the present invention is used.
- terminal electrodes 11 are formed on the glass substrate 1 at a predetermined interval A, while the flexible printed wiring board 3 has an interval narrower than the predetermined interval A of the glass substrate 1.
- a terminal electrode 31 is formed of B.
- the predetermined interval A means the pitch of the terminal electrodes 11 formed of ITO electrodes or the like, and basically does not mean a space between adjacent electrodes, but may be based on the space. Usually, it is 20 to 200 ⁇ m, and it is particularly fine 20 to 60 ⁇ m that the effect of the present invention is effective.
- the flexible printed wiring board 3 one obtained by processing the copper foil of the flexible substrate in which the copper foil is laminated on the polyimide film base into the terminal electrode 31 by etching or the like can be preferably exemplified.
- the interval B narrower than the predetermined interval A means the pitch of the terminal electrodes 31, and basically does not mean a space between adjacent electrodes, but may be based on the space.
- the interval B is narrower than the predetermined interval A, but the level of the narrowness varies depending on the difference in linear expansion coefficient of the glass substrate 1 and the flexible printed wiring board 3, the heating temperature, the heating speed, the pressing force, etc.
- the predetermined interval A is reduced by 0.01 to 1%, preferably 0.1 to 0.3%.
- a heating tool (not shown) is pressed from the flexible printed wiring board 3 side, heated and pressed at a temperature equal to or higher than the minimum melt viscosity, and the anisotropic conductive adhesive 2 is cured, whereby the glass substrate 1 and The two terminal electrodes of the flexible printed wiring board 3 are electrically connected. That is, in this connection step, the flexible printed wiring board 3 is expanded by heating, and the distance B ′ between the terminal electrodes 31 of the flexible printed wiring board 3 is equal to the distance A between the terminal electrodes 11 of the glass substrate 1 as shown in FIG. The terminal electrodes 11 and 31 are electrically connected with a cured product of anisotropic conductive adhesive. Thereby, a connection structure can be obtained.
- a heating tool adjusted so that the temperature of the anisotropic conductive adhesive reaches 150 to 200 ° C. after 4 seconds is 1 to 50 mm / sec, preferably 1 to 10 mm.
- a condition of heating and pressing for 4 seconds or more at that speed is pressed against the anisotropic conductive adhesive 2 at a pressing speed of 1 to 50 mm / sec, particularly 1 to 10 mm / sec when a low speed is intended.
- the conditions include heating and pressing under conditions of 4 seconds or more, preferably 4 to 6 seconds.
- the temperature range (90 to 115 ° C.) indicating the minimum melt viscosity of the anisotropic conductive adhesive 2 is higher than the temperature at the start of heating (for example, room temperature), and the anisotropic conductive adhesive 2 is used. This is lower than the heating temperature (150 to 200 ° C.) for curing. Therefore, under such heating and pressing conditions, the anisotropic conductive adhesive 2 decreases in viscosity after the start of heating, and increases and cures after the minimum melt viscosity (100 to 800 Pa ⁇ s). Such a change in viscosity makes it possible to connect the glass substrate and the flexible printed wiring board with high reliability.
- the pressing speed of the heating tool is set to 1 to 50 mm / sec because if it is slow, the distance between the terminal electrodes of the flexible printed wiring board can be expanded to a predetermined distance, but it is anisotropic before it is fully pressed. This is because the conductive conductive adhesive is cured, and as a result, it is feared that good anisotropic conductive connection cannot be realized. On the other hand, if the speed is increased, there is a concern that the anisotropic conductive adhesive may be cured before the distance between the terminal electrodes of the flexible printed wiring board is expanded to a predetermined distance.
- ⁇ Film-forming resin Bisphenol A / bisphenol F mixed phenoxy resin (Bis-A / Bis-F mixed phenoxy resin: weight average molecular weight 60000) (YP-50, Toto Kasei Co., Ltd.) Bisphenol A / bisphenol F mixed phenoxy resin (Bis-A / Bis-F mixed phenoxy resin: weight average molecular weight 30000) (jER-4110, Japan Epoxy Resins Co., Ltd.) Bisphenol F-type phenoxy resin (Bis-F phenoxy resin: weight average molecular weight 20000) (jER-4007P, Japan Epoxy Resin Co., Ltd.)
- ⁇ Stress relaxation agent> Acrylic rubber (weight average molecular weight 1200000) (SG-600LB, Nagase ChemteX Corporation) Polybutadiene particles (average particle size 0.1 ⁇ m)
- Silane coupling agent Silane coupling agent (KBM-503, Shin-Etsu Chemical Co., Ltd.)
- Conductive particles coated with benzoguanamine particles with nickel-gold plating average particle size 5 ⁇ m, Nippon Chemical Industry Co., Ltd.
- Examples 1 to 7 and Comparative Examples 1 to 4 Among the components shown in Table 1, a radical polymerizable compound, a radical initiator, a film-forming resin, and a coupling agent were dissolved in toluene as a solvent to prepare an insulating adhesive component solution.
- this anisotropic conductive adhesive liquid was applied onto the peeled polyester film so that the thickness after drying was 25 ⁇ m, and dried at 80 ° C. for 5 minutes to form a film-like film.
- An isotropic conductive adhesive was obtained.
- This anisotropic conductive adhesive was cut into strips having a width of 2 mm to obtain anisotropic conductive film samples of Examples 1 to 7 and Comparative Examples 1 to 4.
- ⁇ (1) Conduction resistance value> Using a stainless steel block heating tool, the anisotropic conductive film sample was heated and pressed under the conditions of 180 ° C., pressure 3.5 MPa, and pressing time 4 seconds to create a connection structure, and the conduction resistance value of the connection structure was determined. It was measured. In addition, the speed of the heating tool was performed at five speeds of 50, 30, 10, 1.0, and 0.1 mm / sec, and the conduction resistance value for each heating tool speed was measured.
- connection reliability> Using the connection structure whose conduction resistance value was measured as described above, the conduction resistance was measured after aging treatment for 500 hours under conditions of a temperature of 85 ° C. and a relative humidity of 85%.
- the anisotropic conductive adhesive samples prepared from the blends of Examples 1 to 7 had their minimum melt viscosity adjusted to 100 to 800 Pa ⁇ s. It can be seen that the connection structure using the sample sample had a conduction resistance value of 1 ⁇ or less and a good initial connection state at any heating tool speed in the range of 1.0 to 50 mm / sec. In addition, it can be seen that the resistance values of these examples do not increase beyond 5 ⁇ even with predetermined aging, and the connection reliability is high.
- connection structure using the sample of Comparative Example 1 showed a low conduction resistance value when the heating tool speed was relatively high, but had already reached 10 ⁇ at 1.0 mm / sec.
- the temperature to reach the minimum melt viscosity was appropriate, but the minimum melt viscosity itself was as high as 1000 Pa ⁇ s and the fluidity was inferior. This is not a problem when the heating tool speed is high, but when the pressure tool is low, the interval between the terminal electrodes of the flexible printed wiring board is expanded to a predetermined interval between the terminal electrodes on the glass substrate.
- the minimum melt viscosity of the anisotropic conductive film has been passed and it has already reached the region where the melt viscosity has risen, so that the contact between the glass substrate and both terminal electrodes of the flexible printed wiring board and the conductive particles becomes insufficient. This is considered to indicate that the electrical connection of the connection structure becomes defective.
- connection structure using the sample of Comparative Example 2 voids occurred at any heating tool speed. The generation of a void does not immediately cause an electrical connection failure of the connection structure, but causes a connection failure.
- the sample of Comparative Example 2 was appropriate for the temperature reaching the minimum melt viscosity, but the minimum melt viscosity itself was as low as 70 Pa ⁇ s, and it is considered that voids were generated due to excessive flow.
- connection structure using the sample of Comparative Example 3 had a conduction resistance value of 1 ⁇ or less and a good initial connection state in any heating tool speed range of 1.0 to 50 mm / sec. However, the conduction resistance value significantly increased by the predetermined aging.
- the sample of Comparative Example 3 had an appropriate minimum melt viscosity of 250 Pa ⁇ s, but the temperature to reach the minimum melt viscosity was as high as 120 ° C. Accordingly, it is considered that it takes time to finally cure, causing poor curing, and as a result, the electrical connection of the connection structure is poor.
- connection structure using the sample of Comparative Example 4 entered a low speed region where the heating tool speed was 10 mm / sec, the conduction resistance value increased.
- the sample of Comparative Example 4 had a minimum melt viscosity as high as 900 Pa ⁇ s, and the temperature to reach the minimum melt viscosity was as low as 88 ° C. Accordingly, it is considered that the melt viscosity has already reached the region where the anisotropic conductive adhesive has passed through the minimum melt viscosity. If the heating tool speed is applied to the slow region, contact between the two terminals and the conductive particles is not good. As a result, the electrical connection of the connection structure is considered to be poor.
- the expansion / contraction rate in question was calculated by measuring the length of the flexible printed wiring board before and after thermocompression bonding using a two-dimensional measuring machine.
- the thermal expansion coefficient of the glass substrate (trade name Corning 1737F, manufactured by Corning) used for the connection structure and the polyimide (Kapton EN, manufactured by Toray Dupont), which is the base material of the flexible printed wiring board, is 3.7. ⁇ 10 ⁇ 6 / ° C. and 16 ⁇ 10 ⁇ 6 / ° C.
- the expansion / contraction rate is generally correlated with the temperature of the heating tool, the speed of the heating tool, and the linear expansion coefficient and thickness of the polyimide of the flexible printed wiring board, but from Table 3 in the low speed region (1.0 to 10 mm / sec) It can be seen that the range of the expansion / contraction rate is 0.1 to 0.25%.
- the anisotropic conductive adhesive of the present invention can realize high electrical connection reliability even when the heating tool is contacted and pressed at a slow speed. Therefore, it is useful for anisotropic conductive connection between a glass substrate of a display element such as a liquid crystal panel and a flexible printed wiring board.
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Abstract
Description
最低溶融粘度が100~800Pa・sの範囲であり、最低溶融粘度を示す温度が90~115℃の範囲であることを特徴とする異方性導電接着剤を提供する。
(A)上述の本発明の異方性導電接着剤を前記ガラス基板の端子電極と前記フレキシブルプリント配線板の前記端子電極との間に配置する配置工程;及び
(B)前記フレキシブルプリント配線板側から加熱ツールを押圧して、当該最低溶融粘度以上の温度で加熱押圧して、前記端子電極間を電気的に接続させる接続工程
を有することを特徴とする製造方法を提供する。
まず、既に説明した本発明の異方性導電接着剤を、ガラス基板の端子電極とフレキシブルプリント配線板の端子電極との間に配置する。この配置工程は、本発明の異方性導電接着剤を使用すること以外、従来公知の手法を利用することができる。
次に、フレキシブルプリント配線板3側から加熱ツール(図示せず)を押圧して、最低溶融粘度以上の温度で加熱押圧し、異方性導電接着剤2を硬化させることにより、ガラス基板1とフレキシブルプリント配線板3の両端子電極間を電気的に接続させる。即ち、この接続工程においては、フレキシブルプリント配線板3が加熱により拡張し、図1Bに示すように、フレキシブルプリント配線板3の端子電極31の間隔B′がガラス基板1の端子電極11の間隔Aとほぼ等しくなり、端子電極11と31間とが異方性導電接着剤の硬化物で電気的に接続される。これにより接続構造体を得ることができる。
ジシクロペンタジエンジメタクリレート(DCP、新中村化学工業(株))
ウレタンアクリレート(M-1600、東亞合成(株))
リン含有メタアクリレート(PM2、日本化薬(株))
パーオキシジカーボネート系開始剤(パーロイルL、日油(株))
ジアシルパーオキサイド系開始剤(ナイバーBW、日油(株))
パーオキシケタール系開始剤(パーテトラA、日油(株))
ジアルキルパーオキサイド系開始剤(パークミルD、日油(株))
ビスフェノールA/ビスフェノールF混合フェノキシ樹脂(Bis-A/Bis-F混合フェノキシ樹脂:重量平均分子量60000)(YP-50、東都化成(株))
ビスフェノールA/ビスフェノールF混合フェノキシ樹脂(Bis-A/Bis-F混合フェノキシ樹脂:重量平均分子量30000)(jER-4110,、ジャパンエポキシレジン(株))
ビスフェノールF型フェノキシ樹脂(Bis-Fフェノキシ樹脂:重量平均分子量20000)(jER-4007P、ジャパンエポキシレジン(株))
アクリルゴム(重量平均分子量1200000)(SG-600LB、ナガセケムテックス(株))
ポリブタジエン粒子(平均粒径0.1μm)
シランカップリング剤(KBM-503、信越化学工業(株))
ベンゾグアナミン粒子をニッケル-金めっきで被覆した導電性粒子(平均粒径5μm、日本化学工業(株))
表1に示す配合の成分のうち、ラジカル重合性化合物とラジカル開始剤とフィルム形成樹脂とカップリング剤とを、溶剤であるトルエンに溶解して絶縁性接着成分溶液を調整した。
実施例1~7及び比較例1~4の各異方性導電フィルムサンプルについて、以下に説明するように、「導通抵抗値」、「接続信頼性」、「最低溶融粘度」、「最低溶融粘度に達する温度」、及び接続により発生した「端子間のボイド」を測定評価した。得られた結果を表2に示す。
ステンレスブロックの加熱ツールで、異方性導電フィルムサンプルを、180℃、圧力3.5MPa、押圧時間4秒という条件で加熱押圧して接続構造体を作成し、その接続構造体の導通抵抗値を測定した。なお、加熱ツールの速度は、50、30、10、1.0及び0.1mm/secの5種の速度で行い、これら加熱ツール速度毎の導通抵抗値を測定した。
上述のように導通抵抗値を測定した接続構造体を用い、温度85℃、相対湿度85%の条件で500時間エージング処理後、導通抵抗を測定した。
異方性導電接着剤液体を硬化させることなくトルエンを除いて固化させたものを回転式粘度計に装填し、所定の昇温速度(10℃/min)で上昇させながら溶融粘度を測定した。
<(4)端子電極間のボイド>
各異方性導電フィルムサンプルにより接続された接続構造体について、ガラス基板側から光学顕微鏡を使って目視により、ボイドの有無を観察した。
表1及び表2の結果から、実施例1~実施例7の配合から作成された異方性導電接着剤のサンプルは、その最低溶融粘度が100~800Pa・sに調整されていたため、これら実施例サンプルを使った接続構造体は、加熱ツール速度が1.0~50mm/secの範囲のいずれにおいても、導通抵抗値が1Ω以下となり、初期の接続状態が良好であったことがわかる。また、これら実施例は、所定のエージングによっても、その抵抗値が5Ωを超えて上昇することはなく、接続信頼性が高いことがわかる。
実施例1~実施例7の異方性導電フィルムサンプルを使った接続構造体のうち、実施例2及び実施例3について、その接続構造体におけるフレキシブルプリント配線板の伸縮率を測定した。得られた結果を表3に示す。
2 異方性導電接着剤
3 フレキシブルプリント配線板
11、31 端子電極
Claims (12)
- ラジカル重合性化合物と、ラジカル開始剤と、フィルム形成樹脂とを含有する絶縁性接着成分に、導電性粒子が分散してなる異方性導電接着剤であって、
最低溶融粘度が100~800Pa・sの範囲であり、最低溶融粘度を示す温度が90~115℃の範囲であることを特徴とする異方性導電接着剤。 - (最低溶融粘度)/(最低溶融粘度を示す温度)の値が、0.88~8.8である請求項1記載の異方性導電接着剤。
- 更に、応力緩和剤を含有する請求項1又は2記載の異方性導電接着剤。
- 前記応力緩和剤が、ポリブタジエン粒子である請求項3記載の異方性導電接着剤。
- 該ポリブタジエン粒子を、上記ラジカル重合性化合物とフィルム形成樹脂との合計75質量部に対し、10~30質量部含有する請求項4記載の異方性導電接着剤。
- 該ポリブタジエン粒子が、1×108~1×1010dyn/cm2の弾性率を有する請求項4又は5記載の異方性導電接着剤。
- 該ポリブタジエン粒子が、0.01~5μmの平均粒子径を有する請求項4~6のいずれかに記載の異方性導電接着剤。
- 該フィルム形成樹脂が、重量平均分子量20000~60000のフェノキシ樹脂、又はフェノキシ樹脂とエポキシ樹脂とからなる重量平均分子量20000~60000の混合樹脂の少なくともいずれか一方を含有する請求項1~7のいずれかに記載の異方性導電接着剤。
- 該ラジカル重合性化合物が、ジシクロペンタニル(メタ)アクリルモノマー及びウレタン(メタ)アクリレートオリゴマーの少なくともいずれか一方を含有する請求項1乃至請求項8のいずれかに記載の異方性導電接着剤。
- 所定間隔で端子電極が形成されたガラス基板と、当該所定間隔よりも狭い間隔で端子電極が形成されたフレキシブルプリント配線板とが、異方性導電接着剤を用いて接続されてなる接続構造体の製造方法において、以下の工程(A)及び(B):
(A)請求項1記載の異方性導電接着剤を前記ガラス基板の端子電極と前記フレキシブルプリント配線板の前記端子電極との間に配置する配置工程;及び
(B)前記フレキシブルプリント配線板側から加熱ツールを押圧して、当該最低溶融粘度以上の温度で加熱押圧して、前記端子電極間を電気的に接続させる接続工程
を有することを特徴とする製造方法。 - 工程(B)において、前記異方性導電接着剤の温度が4秒後に150~200℃へ到達するように調整した前記加熱ツールを、1~50mm/secの速度で前記フレキシブルプリント配線板に当接した後、その速度において4秒間以上加熱押圧する請求項10記載の製造方法。
- 工程(B)において、前記異方性導電接着剤の温度が4秒後に150~200℃へ到達するように調整した前記加熱ツールを、1~10mm/secの速度で前記フレキシブルプリント配線板に当接した後、その速度において4秒間以上加熱押圧する請求項10記載の製造方法。
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KR101683312B1 (ko) | 2016-12-06 |
KR20110063500A (ko) | 2011-06-10 |
JP5728803B2 (ja) | 2015-06-03 |
JP5975088B2 (ja) | 2016-08-23 |
JP2010106261A (ja) | 2010-05-13 |
JP2015083681A (ja) | 2015-04-30 |
HK1202132A1 (en) | 2015-09-18 |
CN104059547B (zh) | 2016-08-24 |
HK1156963A1 (en) | 2012-06-22 |
CN104059547A (zh) | 2014-09-24 |
CN102171306B (zh) | 2014-08-13 |
TW201012894A (en) | 2010-04-01 |
CN102171306A (zh) | 2011-08-31 |
TW201406921A (zh) | 2014-02-16 |
TWI548719B (zh) | 2016-09-11 |
TWI541318B (zh) | 2016-07-11 |
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