WO2018181546A1 - 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 - Google Patents

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 Download PDF

Info

Publication number
WO2018181546A1
WO2018181546A1 PCT/JP2018/012922 JP2018012922W WO2018181546A1 WO 2018181546 A1 WO2018181546 A1 WO 2018181546A1 JP 2018012922 W JP2018012922 W JP 2018012922W WO 2018181546 A1 WO2018181546 A1 WO 2018181546A1
Authority
WO
WIPO (PCT)
Prior art keywords
circuit
connection
conductive particles
condition
conductive
Prior art date
Application number
PCT/JP2018/012922
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
智樹 森尻
光晴 松沢
伊澤　弘行
田中　勝
松田　和也
Original Assignee
日立化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to JP2019510018A priority Critical patent/JP7341886B2/ja
Priority to KR1020197030922A priority patent/KR102596306B1/ko
Priority to CN201880021662.3A priority patent/CN110494930B/zh
Publication of WO2018181546A1 publication Critical patent/WO2018181546A1/ja
Priority to JP2022133658A priority patent/JP2022173198A/ja

Links

Images

Classifications

    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

Definitions

  • the present disclosure relates to a method for selecting conductive particles, a circuit connection material, a connection structure and a manufacturing method thereof, and conductive particles.
  • a driving IC is mounted on a glass panel for liquid crystal and OLED (Organic Light-Emitting Diode) display.
  • the system can be broadly classified into two types: COG (Chip-on-Glass) mounting and COF (Chip-on-Flex) mounting.
  • COG Chip-on-Glass
  • COF Chip-on-Flex
  • the driving IC is directly bonded onto the glass panel using an anisotropic conductive adhesive containing conductive particles.
  • COF mounting a driving IC is bonded to a flexible tape having metal wiring, and these are bonded to a glass panel using an anisotropic conductive adhesive containing conductive particles.
  • Anisotropy here means conducting in the pressurizing direction and maintaining insulation in the non-pressurizing direction.
  • An anisotropic conductive adhesive containing conductive particles may be formed in advance in a film shape, and such a film is referred to as an anisotropic conductive film.
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • an electrode formed by laminating a plurality of Cu, Al, Ti and the like on a glass panel, and a composite multilayer electrode further formed with ITO or IZO on the outermost surface have been developed. It is necessary to obtain a stable connection resistance for an electrode using such a material having high flatness and high hardness such as Ti.
  • Patent Document 1 discloses a method for producing conductive fine particles which have base material fine particles and a conductive film formed on the surface thereof, and the conductive film has protrusions protruding on the surface. According to this document, conductive fine particles having a conductive film having protrusions are considered to have excellent conductive reliability.
  • Patent Document 2 discloses conductive particles having substrate particles and a nickel-boron conductive layer provided on the surface thereof. According to this document, since the nickel-boron conductive layer has an appropriate hardness, the oxide film on the surface of the electrode and the conductive particles can be sufficiently eliminated when the member to be connected between the electrodes, and the connection resistance is reduced. It is supposed to be possible.
  • Patent Document 3 discloses conductive particles having resin particles, an electroless metal plating layer covering the surface thereof, and a metal sputter layer excluding Au forming the outermost layer. According to this document, by coating the surface of the resin particles with electroless metal plating, the adhesion with the surface of the resin particles is improved, and by using the outermost layer as a metal sputter layer, good connection reliability can be obtained. It is said that.
  • the conductive particles used in the manufacturing process of the display or the anisotropic conductive film including the conductive particles panel manufacturers have selected and used a variety of materials suitable for the electrode surface material.
  • titanium oxide is formed on the outermost surface of a circuit used for organic EL displays and the like, titanium oxide is formed on the outermost surface, so that conductive particles having a harder plating layer than conventional ones are used.
  • the conductive particles pass through the outermost non-conductive film and come into contact with the conductor portion inside the electrode, thereby realizing low resistance.
  • the conductive particles improved by such a physical technique are applied to, for example, an electrode of an ITO film, there is a problem that the conductive particles before the improvement are less versatile, for example, the resistance may be lower. there were.
  • the electrode circuit of the liquid crystal display and the organic EL display is not uniform.
  • an oxide-based transparent conductive film ITO, IZO, IGZO, IGO, ZnO, etc.
  • an electrode material mainly composed of a metal such as titanium, chromium, aluminum, or tantalum is mainly used.
  • the electrode surface is coated with an organic material such as acrylic resin or an inorganic material such as SiNx or SiOx for the purpose of protecting the electrode portion or providing high reliability.
  • electrode circuits other than the display substrate there are FPC (Flexible Printed Circuit), IC (Integrated Circuit), etc., and various metals such as gold, copper, nickel and the like are used for these electrodes.
  • the present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a method for selecting conductive particles having sufficiently high versatility for circuit electrodes included in circuit members to be connected. Another object of the present disclosure is to provide conductive particles, a circuit connection material using the same, a connection structure, and a manufacturing method thereof.
  • the present disclosure relates to a method for sorting conductive particles.
  • the screening method includes a step of determining whether or not the metal constituting the outermost layer of the conductive particles satisfies the following first condition, and determines whether or not the conductive particles satisfy the following second condition A conductive particle satisfying both the first condition and the second condition is determined to be good.
  • First condition electric conductivity at 20 ° C. of 40 ⁇ 10 6 S / m or less
  • Second condition volume resistivity when load 2 kN is applied is 15 m ⁇ cm or less
  • the second condition is particularly useful for selecting conductive particles that can achieve good connection resistance and have high versatility.
  • the load of 2 kN is presumed to be a state in which the conductive particles are hardly flat. Therefore, it is considered that the resistance value on the surface of the conductive particles can be detected with higher sensitivity than when the load is large.
  • connection portion In an actual connection portion, conductive particles having different flatness ratios are mixed between a pair of facing electrodes due to variations in the particle diameter of the conductive particles or fine irregularities on the electrode surface. That is, some of these conductive particles are not flattened. As described above, even if the conductive particles selected by the method according to the present disclosure have a small flatness, the contribution to the reduction in resistance of the connection portion is large, and a good connection resistance as a whole can be obtained. On the other hand, the conductive particles that do not satisfy one of the first and second conditions have a small contribution to the reduction of the resistance of the connection portion if they are slightly flat. Note that “opposing” in the present specification means that a pair of members are facing each other.
  • a method for selecting conductive particles having sufficiently high versatility for circuit electrodes included in circuit members to be connected Moreover, according to this indication, a conductive particle, a circuit connection material using the same, a connection structure, and a manufacturing method thereof are provided.
  • FIG. 1A is a schematic cross-sectional view showing an enlarged connection portion of a connection structure manufactured using conductive particles selected by the method according to the present disclosure
  • FIG. It is a schematic cross section which expands and shows the connection part of the connection structure manufactured using the electrically-conductive particle which does not satisfy
  • FIG. 2 is a graph showing an example of the measurement result of the volume resistivity.
  • FIG. 3A to FIG. 3C are cross-sectional views schematically showing an example of a method for manufacturing a connection structure.
  • First condition electric conductivity at 20 ° C. of 40 ⁇ 10 6 S / m or less
  • Second condition volume resistivity when load 2 kN is applied is 15 m ⁇ cm or less
  • FIG. 1A is a schematic cross-sectional view showing an enlarged connection portion of a connection structure manufactured using conductive particles selected by the method according to the present embodiment.
  • the conductive particles 1 (conductive particles 1a and 1b) shown in the figure satisfy both the first and second conditions.
  • FIG. 1B is a schematic cross-sectional view showing an enlarged connection portion of a connection structure manufactured using conductive particles 2 (2a, 2b) that do not satisfy one of the first and second conditions. is there.
  • the thickness of the arrow indicates the ease of current flow.
  • the electrical conductivity of the outermost metal layer according to the first condition can be measured using, for example, a conductivity meter (device name: SIGMATEST, manufactured by Nippon Felster Co., Ltd.).
  • a conductivity meter device name: SIGMATEST, manufactured by Nippon Felster Co., Ltd.
  • the element constituting the outermost layer may be analyzed and the electrical conductivity may be specified from the type of the element.
  • the first condition (electrical conductivity at 20 ° C. of the metal layer) may be set to 1 ⁇ 10 6 to 40 ⁇ 10 6 S / m. It may be 10 6 to 40 ⁇ 10 6 S / m.
  • the volume resistivity according to the second condition can be measured using, for example, a powder resistance measurement system (device name: PD51, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Specifically, 2.5 g of conductive particles are charged into a dedicated cell of the device, and the volume resistivity of the conductive particles when a load of 2 kN is applied using the device can be measured. Note that the amount of the conductive particles to be charged may be 0.5 g or more because it is sufficient that the bottom surface of the dedicated cell can be filled. Further, the measurement load can be arbitrarily changed.
  • FIG. 2 is a graph showing an example of the measurement result of the volume resistivity.
  • the results in FIG. 2 are measured every 2 kN from a load of 2 kN to 20 kN.
  • a volume resistivity of 2 kN is used as an index.
  • the second condition volume specific resistance when a load of 2 kN is applied
  • the conductive particles are not particularly limited as long as they have compression characteristics, and examples thereof include core-shell particles having a core particle made of a resin material and a metal layer covering the core particle.
  • the metal layer does not have to cover the entire surface of the core particle, and may be an embodiment in which a part of the surface of the core particle is covered with the metal layer.
  • the metal layer may have a single layer structure or a multilayer structure.
  • the particle size of the conductive particles is generally smaller than the minimum value of the distance between the electrodes of the connected circuit members.
  • the average particle diameter of the conductive particles is preferably larger than the variation in height.
  • the average particle diameter of the conductive particles is preferably 1 to 50 ⁇ m, more preferably 1 to 20 ⁇ m, still more preferably 2 to 10 ⁇ m, and particularly preferably 2 to 6 ⁇ m.
  • “average particle diameter” means a value obtained by observation with a differential scanning electron microscope. That is, one particle is arbitrarily selected, and this is observed with a differential scanning electron microscope to measure the maximum diameter and the minimum diameter. The square root of the product of the maximum diameter and the minimum diameter is defined as the particle diameter of the particle.
  • the particle diameter of 50 arbitrarily selected particles is measured, and the average value thereof is taken to obtain the average particle diameter of the particles.
  • the volume resistivity of the conductive particles to be sorted when a load of 2 kN is applied is 15 m ⁇ cm or less.
  • the volume resistivity is preferably 0.1 to 10 m ⁇ cm, more preferably 0.1 to 7 0.5 m ⁇ cm, and more preferably 0.1 to 5 m ⁇ cm.
  • the compression elastic modulus (20% K value) of the conductive particles when 20% compression displacement is performed at 25 ° C. (20% compression) is preferably 0.5 to 15 GPa, more preferably 1.0 to 10 GPa.
  • the compression hardness K value is an index of the softness of the conductive particles.
  • the 20% K value of the conductive particles is determined by the following method using a Fischer scope H100C (manufactured by Fischer Instrument). One conductive particle spread on the slide glass is compressed at a speed of 0.33 mN / sec. Thus, a stress-strain curve is obtained, and a 20% K value is obtained from this curve.
  • the maximum test load in the compression test is set to 50 mN, for example.
  • the conductive particles in the present embodiment are core-shell type particles and include core particles. Because the conductive particles have core particles, the range of physical property design of the conductive particles themselves is greatly expanded, and the size uniformity of the conductive particles is improved compared to metal powders, etc. It becomes easy to optimize conductive particles.
  • the core particles include various plastic particles.
  • Plastic particles include, for example, acrylic resins such as polymethyl methacrylate and polymethyl acrylate, polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polybutadiene, polystyrene resins, polyester resins, polyurethane resins, polyamide resins, and epoxy resins. From at least one resin selected from the group consisting of resins, polyvinyl butyral resins, rosin resins, terpene resins, phenol resins, guanamine resins, melamine resins, oxazoline resins, carbodiimide resins, silicone resins, etc. What is formed is mentioned.
  • the plastic particles may be a composite of these resins and an inorganic material such as silica.
  • plastic particles from the viewpoint of ease of control of compression recovery rate and compression hardness K value, plastic particles made of a resin obtained by polymerizing one kind of polymerizable monomer having an ethylenically unsaturated group, Alternatively, plastic particles made of a resin obtained by copolymerizing two or more polymerizable monomers having an ethylenically unsaturated group can be used.
  • the average particle size of the plastic particles is preferably 1 to 50 ⁇ m. From the viewpoint of high-density mounting, the average particle size of the plastic particles is more preferably 1 to 20 ⁇ m. In addition, when the unevenness of the electrode surface is uneven, the average particle diameter of the plastic particles is more preferably 2 to 10 ⁇ m from the viewpoint of maintaining a stable connection state.
  • the outermost layer of the conductive particles is composed of a metal layer made of a metal having an electric conductivity at 20 ° C. of 40 ⁇ 10 6 S / m or less.
  • the outermost layer here means a range within 50 nm from the surface of the metal layer.
  • the electric conductivity at 20 ° C. of the metal constituting the outermost layer is 40 ⁇ 10 6 S / m or less, preferably 1 ⁇ 10 6 to 40 ⁇ 10 6 S / m, more preferably 5 ⁇ 10 6 to 20 ⁇ 10 6 S / m.
  • the metal layer may be made of a single metal or may be made of an alloy.
  • the metal having an electric conductivity of 40 ⁇ 10 6 S / m or less include Al, Ti, Cr, Fe, Co, Ni, Zn, Zr, Mo, Pd, In, Sn, W, and Pt.
  • the metal layer is, for example, at least one metal selected from the group consisting of Ni, Ni / Au (a mode in which an Au layer is provided on the Ni layer, the same applies hereinafter), Ni / Pd, Ni / W, Cu, and NiB. Preferably it is formed from.
  • the metal layer is formed by a general method such as plating, vapor deposition, or sputtering, and may be a thin film.
  • a metal layer when forming a metal layer by plating with respect to a plastic particle, it is preferable that a metal layer contains Ni, Pd, or W from a viewpoint of the plating property with respect to a plastic. Furthermore, it is preferable to eliminate the resin between the electrode and the particles at the time of pressure bonding, and a lower resistance can be obtained, so that the metal layer preferably contains Ni. In addition to being excellent in resin exclusion at the time of press bonding, Ni is superior in plating and corrosion resistance compared to Au, Cu and Ag, which have high electrical conductivity, and also in terms of supply stability and price. There are advantages.
  • the thickness of the metal layer is preferably 10 to 1000 nm, more preferably 20 to 500 nm, and still more preferably 50 to 250 nm from the viewpoint of achieving a balance between conductivity and price.
  • Conductive particles are formed by attaching an insulating material layer (eg, organic film) or insulating fine particles (eg, organic fine particles or inorganic fine particles) to the outside of the metal layer from the viewpoint of improving insulation between adjacent electrodes.
  • You may have an adhesion layer.
  • the thickness of the adhesion layer is preferably about 50 to 1000 nm.
  • the thicknesses of the metal layer and the adhesion layer can be measured by, for example, a scanning electron microscope (SEM), a transmission electron microscope (TEM), an optical microscope, or the like.
  • the metal layer may have protrusions on the surface. By having protrusions on the metal layer, it is possible to eliminate the resin at the time of crimping, to increase the number of contact points with the electrode, and to further contact the inside of the electrode with the conductive particles. Resistance can be achieved.
  • the circuit connection material is used for bonding circuit members together and electrically connecting circuit electrodes (for example, connection terminals) included in each circuit member.
  • the circuit connecting material includes an adhesive component that is cured by light or heat, and conductive particles dispersed in the adhesive component, and the conductive particles satisfy both the first and second conditions. .
  • the circuit connection material is prepared by dispersing conductive particles in the adhesive component.
  • the paste-like adhesive composition may be used as it is, or an anisotropic conductive film obtained by forming this into a film may be used.
  • the blending amount of the conductive particles is 0.1 to 30 volumes when the total volume of the circuit connecting material is 100 parts by volume from the viewpoint of balancing the conductivity between the counter electrodes and the insulation between the adjacent electrodes in a balanced manner. Part, preferably 0.5 to 15 parts by volume, more preferably 1 to 7.5 parts by volume.
  • the compounding amount of the adhesive component is a circuit connecting material from the viewpoint of maintaining the gap between the electrodes at the time of circuit connection and after connection, and ensuring the strength and elasticity necessary for providing excellent connection reliability.
  • the total mass is 100 parts by mass, it is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and still more preferably 30 to 70 parts by mass.
  • the adhesive component is not particularly limited.
  • a composition containing an epoxy resin and an epoxy resin latent curing agent hereinafter referred to as “first composition”
  • first composition a composition containing an epoxy resin and an epoxy resin latent curing agent
  • second composition a composition containing a curing agent that generates water
  • the epoxy resin contained in the first composition is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol.
  • Examples thereof include F novolac type epoxy resins, alicyclic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and aliphatic chain epoxy resins. These epoxy resins may be halogenated or hydrogenated. Two or more of these epoxy resins may be used in combination.
  • the latent curing agent contained in the first composition is not particularly limited as long as it can cure the epoxy resin.
  • latent curing agents include anionic polymerizable catalyst-type curing agents and cationic polymerizable agents. Catalyst-type curing agents, polyaddition-type curing agents, and the like. These can be used alone or as a mixture of two or more. Of these, anionic or cationic polymerizable catalyst-type curing agents are preferred because they are excellent in rapid curability and do not require chemical equivalent considerations.
  • anionic or cationic polymerizable catalyst-type curing agent examples include imidazole curing agent, hydrazide curing agent, boron trifluoride-amine complex, sulfonium salt, amine imide, diaminomaleonitrile, melamine and its derivatives, polyamine salt, dicyandiamide These modifications can also be used.
  • the polyaddition type curing agent examples include polyamines, polymercaptans, polyphenols, and acid anhydrides.
  • the epoxy resin is cured by heating at a medium temperature of about 160 ° C. to 200 ° C. for several tens of seconds to several hours. For this reason, pot life (pot life) can be made relatively long.
  • the cationic polymerizable catalyst-type curing agent for example, photosensitive onium salts (such as aromatic diazonium salts and aromatic sulfonium salts) that cure the epoxy resin by energy ray irradiation are preferable.
  • photosensitive onium salts such as aromatic diazonium salts and aromatic sulfonium salts
  • the blending amount of the latent curing agent contained in the first composition is preferably 20 to 80 parts by mass with respect to 100 parts by mass in total of the epoxy resin and the film forming material to be blended if necessary, and preferably 30 to 70 parts by mass. Part by mass is more preferable.
  • the radical polymerizable substance contained in the second composition is a substance having a functional group that is polymerized by radicals.
  • examples of such radically polymerizable substances include acrylate (including corresponding methacrylates; the same shall apply hereinafter) compounds, acryloxy (including corresponding methacryloxy; the same shall apply hereinafter) compounds, maleimide compounds, citraconic imide resins, nadiimide resins, and the like. It is done.
  • the radically polymerizable substance may be used in a monomer or oligomer state, and the monomer and oligomer may be used in combination.
  • the acrylate compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, 2-hydroxy-1,3- Diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate , Tris (acryloyloxyethyl) isocyanurate, urethane acrylate and the like.
  • the acrylate compound preferably has at least one substituent selected from the group consisting of a dicyclopentenyl group, a tricyclodecanyl group, and a triazine ring.
  • a compound described in International Publication No. 2009/063827 can be preferably used. These are used individually by 1 type or in combination of 2 or more types.
  • radical polymerizable substance having a phosphate ester structure represented by the following formula (I) it is preferable to use a radical polymerizable substance having a phosphate ester structure represented by the following formula (I) in combination with the radical polymerizable substance.
  • a radical polymerizable substance having a phosphate ester structure represented by the following formula (I) since the adhesive strength to the surface of an inorganic material such as metal is improved, it is suitable for bonding circuit electrodes.
  • n an integer of 1 to 3.
  • a radical polymerizable substance having a phosphate ester structure can be obtained by reacting anhydrous phosphoric acid with 2-hydroxyethyl (meth) acrylate.
  • Specific examples of the radical polymerizable substance having a phosphate structure include mono (2-methacryloyloxyethyl) acid phosphate, di (2-methacryloyloxyethyl) acid phosphate, and the like. These can be used alone or in admixture of two or more.
  • the blending amount of the radically polymerizable substance having a phosphate ester structure represented by the above formula (I) is 0.01 to 50 with respect to 100 parts by mass in total of the radically polymerizable substance and the film forming material to be blended if necessary.
  • the amount is preferably part by mass, and more preferably 0.5 to 5 parts by mass.
  • the above radical polymerizable substance can be used in combination with allyl acrylate.
  • the compounding amount of allyl acrylate is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the radical polymerizable substance and the film forming material to be compounded as necessary. More preferable is 5 parts by mass.
  • the curing agent that generates a free radical by heating which is contained in the second composition, is a curing agent that decomposes by heating to generate a free radical.
  • a curing agent examples include peroxides and azo compounds.
  • Such a curing agent is appropriately selected depending on the intended connection temperature, connection time, pot life, and the like. From the viewpoint of high reactivity and improvement in pot life, organic peroxides having a half-life of 10 hours at a temperature of 40 ° C. or more and a half-life of 1 minute at a temperature of 180 ° C. or less are preferred. An organic peroxide having a temperature of 60 ° C. or higher and a half-life of 1 minute is 170 ° C. or lower is more preferable.
  • the amount of the curing agent is 2 to 10 parts by mass with respect to a total of 100 parts by mass of the radical polymerizable substance and the film-forming material to be blended as necessary.
  • the amount is preferably 4 to 8 parts by mass. Thereby, sufficient reaction rate can be obtained.
  • the compounding amount of the curing agent is 0.05 to 20 parts by mass with respect to 100 parts by mass in total of the radical polymerizable substance and the film forming material to be blended as necessary.
  • the amount is preferably 0.1 to 10 parts by mass.
  • curing agents that generate free radicals upon heating contained in the second composition are diacyl peroxide, peroxydicarbonate, peroxyester peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide. Etc. Further, from the viewpoint of suppressing the corrosion of the circuit electrode, a curing agent having a concentration of chlorine ions and organic acid of 5000 ppm or less is preferable, and a curing agent with less organic acid generated after thermal decomposition is more preferable. Specific examples of such curing agents include peroxyesters, dialkyl peroxides, hydroperoxides, silyl peroxides, and the like, and curing agents selected from peroxyesters that provide high reactivity are more preferable. In addition, the said hardening
  • Peroxyesters include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, and t-hexyl.
  • curing agents can be used alone or in admixture of two or more, and further, a decomposition accelerator, a decomposition inhibitor and the like may be mixed and used. Further, these curing agents may be coated with a polyurethane-based or polyester-based polymer substance to form microcapsules. A microencapsulated curing agent is preferred because the pot life is extended.
  • a film forming material may be added as necessary.
  • Film-forming material means that when a liquid material is solidified and the composition composition is made into a film shape, it is easy to handle the film in a normal state (normal temperature and normal pressure), and does not easily tear, break or stick. Mechanical properties and the like are imparted to the film.
  • the film forming material include phenoxy resin, polyvinyl formal resin, polystyrene resin, polyvinyl butyral resin, polyester resin, polyamide resin, xylene resin, polyurethane resin and the like.
  • a phenoxy resin is preferable because of excellent adhesiveness, compatibility, heat resistance, and mechanical strength.
  • the phenoxy resin is a resin obtained by reacting a bifunctional phenol and epihalohydrin until they are polymerized, or by polyaddition of a bifunctional epoxy resin and a bifunctional phenol.
  • the phenoxy resin is prepared by reacting, for example, 1 mol of a bifunctional phenol and 0.985 to 1.015 mol of epihalohydrin in a non-reactive solvent at a temperature of 40 to 120 ° C. in the presence of a catalyst such as an alkali metal hydroxide. Can be obtained.
  • bifunctional epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, methyl substituted biphenyl diglycidyl ether, and the like.
  • Bifunctional phenols have two phenolic hydroxyl groups.
  • examples of the bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluorene, methyl-substituted bisphenol fluorene, bisphenols such as dihydroxybiphenyl and methyl-substituted dihydroxybiphenyl.
  • the phenoxy resin may be modified (for example, epoxy-modified) with a radical polymerizable functional group or other reactive compound.
  • the blending amount of the film forming material is preferably 10 to 90 parts by mass, and more preferably 20 to 60 parts by mass when the total mass of the circuit connecting material is 100 parts by mass.
  • the circuit connection material of this embodiment may further contain a polymer or copolymer containing at least one of acrylic acid, acrylic acid ester, methacrylic acid ester, and acrylonitrile as a monomer component.
  • the circuit connection material since it is excellent in stress relaxation, it is preferable that the circuit connection material includes a glycidyl acrylate-containing copolymer and / or a copolymer acrylic rubber containing glycidyl methacrylate.
  • the weight average molecular weight of these acrylic rubbers is preferably 200,000 or more from the viewpoint of increasing the cohesive strength of the adhesive composition.
  • the circuit connection material of the present embodiment further includes fine rubber particles, fillers, softeners, accelerators, anti-aging agents, colorants, flame retardants, thixotropic agents, coupling agents, phenol resins, melamine resins, isocyanates. Etc. can also be contained.
  • the rubber fine particles have an average particle size not more than twice the average particle size of the conductive particles to be blended, and the storage elastic modulus at room temperature (25 ° C.) of the conductive particles and the adhesive composition at room temperature. It is preferable that it is less than 1/2 of the rate.
  • the material of the rubber fine particles is silicone, acrylic emulsion, SBR, NBR or polybutadiene rubber, it is preferable to use them alone or in combination of two or more. These three-dimensionally crosslinked rubber fine particles are excellent in solvent resistance and are easily dispersed in the adhesive composition.
  • the filler can improve the connection reliability of the electrical characteristics between the circuit electrodes.
  • the filler for example, those having an average particle size of 1 ⁇ 2 or less of the average particle size of the conductive particles can be suitably used.
  • grains which do not have electroconductivity if it is below the average particle diameter of the particle
  • the blending amount of the filler is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the adhesive composition. When the blending amount is 60 parts by mass or less, there is a tendency that the effect of improving the connection reliability can be obtained more sufficiently, and when it is 5 parts by mass or more, there is a tendency that the effect of adding the filler can be sufficiently obtained. .
  • a compound containing an amino group, a vinyl group, an acryloyl group, an epoxy group or an isocyanate group is preferable because the adhesiveness is improved.
  • the circuit connection material melts and flows at the time of connection to obtain the connection of the opposing circuit electrodes, and then hardens to maintain the connection.
  • the fluidity of the circuit connection material is an important factor. As an index indicating this, for example, the following can be cited. That is, when a circuit connection material of 5 mm ⁇ 5 mm with a thickness of 35 ⁇ m is sandwiched between two glass plates of 15 mm ⁇ 15 mm with a thickness of 0.7 mm, and heating and pressurization are performed under conditions of 170 ° C., 2 MPa, 10 seconds
  • the value of fluidity (B) / (A) expressed using the area (A) of the main surface of the circuit connecting material before heating and pressing and the area (B) of the main surface after heating and pressing is 1.
  • It is preferably from 3 to 3.0, more preferably from 1.5 to 2.5. If it is 1.3 or more, the fluidity is suitable, and it tends to be easy to obtain a good connection, and if it is 3.0 or less, bubbles tend not to be generated and the reliability tends to be excellent.
  • the elastic modulus at 40 ° C. after curing of the circuit connecting material is preferably 100 to 3000 MPa, and more preferably 500 to 2000 MPa.
  • the elastic modulus of the circuit connection material after curing can be measured using, for example, a dynamic viscoelasticity measuring device (DVE, DMA, etc.).
  • the circuit connection material of this embodiment is COG connection (Chip on Glass), FOB (Flex on Board) connection, FOG (Flex on Glass) connection, FOF (Flex on Flex) connection, FOP (Flex on Polymer) connection, COP. It is suitably used for (Chip on Polymer) connection, COF (Chip on Flex) connection, and the like.
  • COG connection is, for example, a method of connecting an IC to an organic EL panel or an LCD panel, and a circuit electrode formed on the IC and a circuit electrode formed on a glass substrate constituting the organic EL panel or LCD panel.
  • the FOB connection refers to a connection between a circuit electrode formed on a flexible substrate and a circuit electrode formed on a printed wiring board, typified by TCP (Tape Carrier Package), COF, and FPC.
  • the FOG connection refers to a connection between a circuit electrode formed on a flexible substrate and a circuit electrode formed on a glass substrate constituting an organic EL panel or LCD panel, as typified by TCP, COF, and FPC.
  • the FOF connection refers to a connection between a circuit electrode formed on a flexible substrate and a circuit electrode formed on the flexible substrate, typified by TCP, COF, and FPC, for example.
  • FOP connection refers to connection between a circuit electrode formed on a flexible substrate and a circuit electrode formed on a polymer substrate constituting an organic EL panel or LCD panel.
  • COP connection refers to connection between a circuit electrode formed on an IC and a circuit electrode formed on a plastic substrate.
  • COF connection refers to connection between a circuit electrode formed on an IC and a circuit electrode formed on a flexible substrate.
  • the circuit connection structure of this embodiment includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, a first circuit member, and a second circuit member. And a connecting portion made of a cured product of the above-described circuit connecting material.
  • circuit electrode materials include Ti, Al, Mo, Co, Cu, Cr, Sn, Zn, Ga, In, Ni, Au, Ag, V, Sb, Bi, Re, Ta, Nb, W or the like can be used.
  • the thickness of the circuit electrode is preferably 100 to 5000 nm, and more preferably 100 to 2500 nm, from the viewpoint of balancing connection resistance and price. Further, the lower limit can be set to 500 nm.
  • the circuit connection structure of the present embodiment includes a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode, and the first circuit electrode and the second circuit electrode. Are arranged so as to face each other, a circuit connecting material is interposed between the first circuit electrode and the second circuit electrode which are arranged to face each other, and heated and pressurized to thereby form the first circuit electrode and the second circuit electrode. Are electrically connected to each other.
  • the circuit connection material of this embodiment is useful as a material for bonding electrical circuits.
  • examples of the circuit member include chip parts such as a semiconductor chip, a resistor chip, and a capacitor chip, and a substrate such as a printed board.
  • These circuit members are usually provided with a large number (in some cases a single electrode) of the above-mentioned circuit electrodes.
  • the circuit electrodes arranged to face each other can be electrically connected to each other. Connecting. At this time, the circuit electrodes arranged opposite to each other are electrically connected through conductive particles contained in the circuit connection material, while insulation between adjacent circuit electrodes is maintained.
  • the circuit connection material of this embodiment exhibits anisotropic conductivity.
  • FIGS. 3 (a) to 3 (c) An embodiment of a method of manufacturing a circuit connection structure will be described with reference to FIGS. 3 (a) to 3 (c).
  • 3A is a process cross-sectional view before connecting circuit members
  • FIG. 3B is a process cross-sectional view when connecting circuit members
  • FIG. It is process sectional drawing after connecting.
  • a circuit member 20 having a circuit electrode 21a and a circuit board 21b provided on an organic EL panel 21, and a circuit member 30 having a circuit electrode 31a provided on a substrate 31 are provided.
  • molded by the film form is mounted on the circuit electrode 21a.
  • the substrate 31 on which the circuit electrode 31a is provided is aligned on the circuit connection material 5 while positioning the circuit electrode 21a and the circuit electrode 31a so as to face each other.
  • the circuit connection material 5 is interposed between the circuit electrode 21a and the circuit electrode 31a.
  • the circuit electrodes 21a and 31a have a structure (not shown) in which a plurality of electrodes are arranged in the depth direction. Since the circuit connection material 5 is in the form of a film, it is easy to handle. For this reason, the circuit connection material 5 can be easily interposed between the circuit electrode 21a and the circuit electrode 31a, and the connection work between the circuit member 20 and the circuit member 30 can be facilitated.
  • the circuit connection material 5 is pressed in the direction of the arrow A in FIG. 3B through the organic EL panel 21 and the substrate 31 while being heated to perform a curing process.
  • a circuit connection structure 50 in which the circuit members 20 and 30 are connected to each other via the cured product 5a of the circuit connection material as shown in FIG. 3C is obtained.
  • a method for the curing treatment one or both of heating and light irradiation can be employed depending on the adhesive composition to be used.
  • Conductive Particles Eleven types of conductive particles A to K shown in Table 1 below were prepared. Each of these conductive particles is a core-shell particle composed of a core made of plastic particles and a metal layer (nickel layer) covering the core particle. The electrical conductivity of nickel is 14.5 ⁇ 10 6 S / m. Of the conductive particles A to K, the conductive particles A to E and the conductive particles H and J satisfy both the first and second conditions.
  • phenoxy resin product name: PKHC, manufactured by Union Carbide Co., Ltd., weight average molecular weight 5000
  • connection structure (electrode outermost surface: titanium)
  • An anisotropic conductive film with a PET film was cut into a predetermined size (width 1.5 mm ⁇ length 3 cm).
  • the surface on which the anisotropic conductive film is formed is transferred from the outermost surface onto a glass substrate (thickness 0.7 mm) coated with titanium (film thickness 50 nm) and aluminum (film thickness 250 nm) in this order. did.
  • the transfer conditions were 70 ° C. and 1 MPa for 2 seconds.
  • a flexible circuit board (FPC) having 600 tin-plated copper circuits with a pitch of 50 ⁇ m and a thickness of 8 ⁇ m was temporarily fixed on the anisotropic conductive film. Temporary fixing was performed at 24 ° C. and 0.5 MPa for 1 second. Next, this is installed in the main pressure bonding apparatus, and a 200 ⁇ m-thick silicone rubber sheet is used as a cushioning material. From the FPC side, heat and pressure are applied with a heat tool at 170 ° C. and 3 MPa for 6 seconds to connect over a width of 1.5 mm. did. Thereby, a connection structure was obtained.
  • FPC flexible circuit board
  • connection structure electrode outermost surface: ITO
  • connection structure (electrode outermost surface: IZO) Instead of the glass substrate coated in order of titanium and aluminum from the outermost surface, a glass substrate coated in the order of IZO (film thickness of 100 nm), Cr (film thickness of 50 nm) and aluminum (film thickness of 200 nm) from the outermost surface is used.
  • IZO glass substrate coated in the order of IZO (film thickness of 100 nm), Cr (film thickness of 50 nm) and aluminum (film thickness of 200 nm) from the outermost surface is used.
  • a connection structure was obtained in the same manner as described above except that
  • connection resistance of the obtained two types of connection structures was measured as follows.
  • the resistance value between adjacent circuits of the FPC including the connection part of the connection structure was measured with a multimeter (device name: TR6845, manufactured by Advantest Corporation).
  • 40 resistances between adjacent circuits were measured to obtain an average value, and this was used as a connection resistance.
  • Table 3 shows the results.
  • a method for selecting conductive particles having sufficiently high versatility for circuit electrodes included in circuit members to be connected Moreover, according to this indication, a conductive particle, a circuit connection material using the same, a connection structure, and a manufacturing method thereof are provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electrical Connectors (AREA)
  • Wire Bonding (AREA)
PCT/JP2018/012922 2017-03-29 2018-03-28 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 WO2018181546A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2019510018A JP7341886B2 (ja) 2017-03-29 2018-03-28 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
KR1020197030922A KR102596306B1 (ko) 2017-03-29 2018-03-28 도전 입자의 선별 방법, 회로 접속 재료, 접속 구조체 및 그의 제조 방법, 그리고 도전 입자
CN201880021662.3A CN110494930B (zh) 2017-03-29 2018-03-28 导电粒子的分选方法、电路连接材料、连接结构体及其制造方法、以及导电粒子
JP2022133658A JP2022173198A (ja) 2017-03-29 2022-08-24 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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017066022 2017-03-29
JP2017-066022 2017-03-29

Publications (1)

Publication Number Publication Date
WO2018181546A1 true WO2018181546A1 (ja) 2018-10-04

Family

ID=63677389

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/012922 WO2018181546A1 (ja) 2017-03-29 2018-03-28 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

Country Status (5)

Country Link
JP (2) JP7341886B2 (zh)
KR (1) KR102596306B1 (zh)
CN (2) CN110494930B (zh)
TW (1) TW201841169A (zh)
WO (1) WO2018181546A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023149294A1 (ja) * 2022-02-03 2023-08-10 積水化学工業株式会社 導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021178913A (ja) * 2020-05-13 2021-11-18 昭和電工マテリアルズ株式会社 導電性接着剤、回路接続構造体の製造方法及び回路接続構造体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004165019A (ja) * 2002-11-13 2004-06-10 Sekisui Chem Co Ltd 導電性微粒子および異方導電材料
JP4563110B2 (ja) * 2004-08-20 2010-10-13 積水化学工業株式会社 導電性微粒子の製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5940760B2 (ja) 2010-05-19 2016-06-29 積水化学工業株式会社 導電性粒子、異方性導電材料及び接続構造体
JP2012164454A (ja) 2011-02-04 2012-08-30 Sony Chemical & Information Device Corp 導電性粒子及びこれを用いた異方性導電材料
JP2014149918A (ja) * 2011-06-06 2014-08-21 Hitachi Chemical Co Ltd フィルム状回路接続材料及び回路接続構造体
JP6379761B2 (ja) * 2014-07-09 2018-08-29 日立化成株式会社 導電粒子、絶縁被覆導電粒子、異方導電性接着剤、接続構造体及び導電粒子の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004165019A (ja) * 2002-11-13 2004-06-10 Sekisui Chem Co Ltd 導電性微粒子および異方導電材料
JP4563110B2 (ja) * 2004-08-20 2010-10-13 積水化学工業株式会社 導電性微粒子の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023149294A1 (ja) * 2022-02-03 2023-08-10 積水化学工業株式会社 導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体

Also Published As

Publication number Publication date
KR102596306B1 (ko) 2023-10-30
TW201841169A (zh) 2018-11-16
CN110494930A (zh) 2019-11-22
JPWO2018181546A1 (ja) 2020-02-06
KR20190133023A (ko) 2019-11-29
JP2022173198A (ja) 2022-11-18
CN113823459A (zh) 2021-12-21
JP7341886B2 (ja) 2023-09-11
CN110494930B (zh) 2021-10-01

Similar Documents

Publication Publication Date Title
JP4862921B2 (ja) 回路接続材料、回路接続構造体及びその製造方法
JP5737278B2 (ja) 回路接続材料、接続体、及び接続体を製造する方法
JP5067355B2 (ja) 回路接続材料及び回路部材の接続構造
JP4862944B2 (ja) 回路接続材料
JP4752986B1 (ja) 回路接続用接着フィルム及び回路接続構造体
KR101929073B1 (ko) 필름상 회로 접속 재료 및 회로 접속 구조체
JP2022173198A (ja) 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
JP2013055058A (ja) 回路接続材料、及び回路部材の接続構造
JP6337630B2 (ja) 回路接続材料及び回路接続構造体
JP2019065062A (ja) 導電性接着フィルム
JP4945881B2 (ja) 回路接続用支持体付接着剤、及びそれを用いた回路接続構造体
JP7006029B2 (ja) 回路接続用接着剤組成物及び構造体
JP2012160546A (ja) 回路接続用接着フィルム及び回路接続構造体
JP3937299B2 (ja) 支持体つき接着剤及びそれを用いた回路接続構造体
WO2021230212A1 (ja) 導電性接着剤、回路接続構造体の製造方法及び回路接続構造体
JP2011054988A (ja) 回路接続材料
JP2009289729A (ja) 異方導電フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18776138

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019510018

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20197030922

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18776138

Country of ref document: EP

Kind code of ref document: A1