WO2021025112A1 - Resin particle, electrically conductive particle, electrically conductive material, and connected structure - Google Patents

Resin particle, electrically conductive particle, electrically conductive material, and connected structure Download PDF

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Publication number
WO2021025112A1
WO2021025112A1 PCT/JP2020/030184 JP2020030184W WO2021025112A1 WO 2021025112 A1 WO2021025112 A1 WO 2021025112A1 JP 2020030184 W JP2020030184 W JP 2020030184W WO 2021025112 A1 WO2021025112 A1 WO 2021025112A1
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Prior art keywords
conductive
resin particles
particles
resin
compression
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PCT/JP2020/030184
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French (fr)
Japanese (ja)
Inventor
弘幸 森田
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積水化学工業株式会社
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Priority to JP2021537376A priority Critical patent/JPWO2021025112A1/ja
Publication of WO2021025112A1 publication Critical patent/WO2021025112A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48135—Connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/48137—Connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being arranged next to each other, e.g. on a common substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item

Definitions

  • the present invention relates to resin particles having good compression characteristics.
  • the present invention also relates to conductive particles, conductive materials and connecting structures using the above resin particles.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in the binder.
  • the anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit board (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure.
  • connection target members such as a flexible printed circuit board (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure.
  • FPC flexible printed circuit board
  • conductive particles conductive particles having resin particles and conductive portions arranged on the surface of the resin particles may be used.
  • the liquid crystal display element is configured by arranging a liquid crystal between two glass substrates.
  • a spacer is used as a gap control material in order to keep the distance (gap) between the two glass substrates uniform and constant.
  • Resin particles are generally used as the spacer.
  • Patent Document 1 a resin (A) containing an acidic group and a group having an ethylenically unsaturated bond in a side chain, and two or more polymerizable substituents having an ethylenically unsaturated bond are described.
  • a photosensitive composition for a color filter containing at least a polymerizable compound (B) containing a divalent or higher valent ring structure-containing group bonded to the polymerizable substituent and a photopolymerization initiator (C) is disclosed. ing.
  • Patent Document 1 describes that it is preferable that this photosensitive composition contains fine particles (D), and that a photospacer can be formed by using the photosensitive composition.
  • the deformation recovery rate of the photo spacer formed by the photosensitive composition is evaluated, it is only described that the deformation recovery rate is preferably high.
  • the conductive particles when conducting conductive connections between electrodes, the conductive particles may not be sufficiently deformed, or the compressed conductive particles may act to return to their original shape. In this case, the contact area between the conductive particles and the electrode (adhesion) is not sufficiently large, or peeling occurs at the interface between the conductive particles and the electrode, resulting in high connection resistance and conduction. Reliability is reduced.
  • the contact area and frictional resistance between the resin particles and the member to be connected are not sufficiently large, and the resin particles are fixed in a predetermined position by rolling or the like. It may not be done. In this case, peeling may occur at the interface between the resin particles and the member to be connected, and the thickness between the members to be connected may not be uniformly controlled, and the function as a spacer may not be sufficiently exhibited.
  • the resin particles are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then released to 25 ° C. when released from the compression. Therefore, the resin particles are provided in which the coefficient of variation of the aspect ratio of the resin particles after compression / release observed from a direction orthogonal to the compression direction is 10% or less.
  • the resin particles can be thermoset by heating.
  • the thermal decomposition temperature is 200 ° C. or higher and 350 ° C. or lower.
  • the compression elastic modulus of when compressed 10% it is 100 N / mm 2 or more 3500 N / mm 2 or less.
  • the compressive elastic modulus when compressed by 30% is 100 N / mm 2 or more and 3000 N / mm 2 or less.
  • the aspect ratio of the resin particles after compression / release observed from a direction orthogonal to the compression direction is 1.1 or more.
  • the resin particles are used as spacers, adhesives for electronic parts, or used to obtain conductive particles having a conductive portion. , Used as a material for laminated molding.
  • the resin particles are used as a spacer for a liquid crystal display element, an adhesive for an electronic component, or a conductive particle having a conductive portion. Used for.
  • a conductive particle including the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles is provided.
  • the conductive particles further include an insulating substance disposed on the outer surface of the conductive portion.
  • the conductive particles have protrusions on the outer surface of the conductive portion.
  • a conductive material containing conductive particles and a binder resin wherein the conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles.
  • a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member are provided.
  • a first connection target member having a first electrode on the surface
  • a second connection target member having a second electrode on the surface
  • the first connection target member and the above. It is provided with a connecting portion connecting the second connection target member, and the connecting portion is formed of conductive particles or a conductive material containing the conductive particles and a binder resin.
  • the conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles, and the first electrode and the second electrode are electrically formed by the conductive particles.
  • a connected, connected structure is provided.
  • the resin particles according to the present invention are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then when released from compression, they are orthogonal to the compression direction at 25 ° C.
  • the coefficient of variation of the aspect ratio of the resin particles after compression / release observed from the direction is 10% or less. Since the resin particles according to the present invention have the above-mentioned structure, the contact area and frictional resistance between the resin particles or the particles using the resin particles and the adherend can be increased, and therefore, the resin particles. Alternatively, it is possible to suppress interfacial peeling between the particles using the resin particles and the adherend.
  • FIG. 1 is a cross-sectional view showing resin particles according to the first embodiment of the present invention
  • FIG. 1A is a cross-sectional view showing resin particles before compression
  • FIG. 1B is compression. It is sectional drawing which shows the resin particle after release.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing the conductive particles according to the second embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing the conductive particles according to the third embodiment of the present invention.
  • FIG. 5 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention.
  • FIG. 6 is a cross-sectional view showing an example of an electronic component device using the resin particles according to the present invention.
  • FIG. 7 is an enlarged cross-sectional view showing a joint portion in the electronic component device shown in FIG.
  • FIG. 8A is a typical electron micrograph of the resin particles (resin particles before heat curing)
  • FIG. 8B is a typical electron micrograph of the resin particles after compression and release.
  • FIG. 9 is an electron micrograph of the resin particles after compression release in Example 8.
  • FIG. 10 (a) is an electron micrograph of the resin particles after compression and release in Comparative Example 1
  • FIG. 10 (b) is an electron micrograph of the resin particles after compression and release in Comparative Example 2.
  • FIG. (C) is an electron micrograph of the resin particles after compression and release in Comparative Example 3.
  • the resin particles according to the present invention are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then released from compression at 25 ° C. in a direction orthogonal to the compression direction.
  • the coefficient of variation of the aspect ratio of the resin particles after compression / release observed from is 10% or less.
  • the resin particles according to the present invention have the above-mentioned structure, the contact area and frictional resistance between the resin particles or the particles using the resin particles and the adherend can be increased, and therefore, the resin particles. Alternatively, it is possible to suppress interfacial peeling between the particles using the resin particles and the adherend.
  • the resin particles according to the present invention can be thermoset by heating.
  • the resin particles according to the present invention can be thermoset by heating.
  • the resin particles (resin particles before thermosetting) according to the present invention are not completely thermoset, can maintain a good compressed shape when heat-compressed, and have a plurality of resin particles. The compressed shape can be well aligned. Whether or not the resin particles according to the present invention can be thermoset can be confirmed as follows.
  • the resin particles before thermosetting are heated at 200 ° C. for 1 hour and then cooled at 25 ° C. for 1 hour. From the compressive elastic modulus (10% K value) when the resin particles after heating and cooling are compressed by 10% and the compressive elastic modulus (10% K value) when the resin particles before thermosetting are compressed by 10%, The rate of change in compressive elastic modulus before and after thermosetting is calculated by the following formula. When the rate of change in elastic modulus before and after thermosetting calculated by the following formula is 105% or more, it is considered that thermosetting by heating has occurred, and the particles are thermosetting by heating.
  • the 10% K value of the resin particles can be measured by the method described later.
  • Rate of change in compressive elastic modulus before and after thermosetting (10% K value of resin particles after heating and cooling) / (10% K value of resin particles before thermosetting) x 100
  • the conductive particles according to the present invention are used as conductive particles in which a conductive portion is formed on the surface of the resin particles, the conductive particles are good at the time of thermal pressure bonding between the conductive particles and the electrode (adhesion). Since it is deformed into a shape and the compressed shape is maintained even after thermal pressure bonding, the contact area between the conductive particles and the electrode can be increased. Therefore, it is possible to suppress the interfacial peeling between the conductive particles and the electrode, and further, it is possible to effectively suppress the damage to the electrode. Further, when the electrodes are electrically connected, the adhesion between the resin particles and the conductive portion in the conductive particles can be improved.
  • connection resistance of the connection structure in which the electrodes are electrically connected by the conductive particles can be effectively lowered, and the continuity reliability can be improved. Can be enhanced. Further, even if the connection structure is left for a long time under high temperature and high humidity conditions, the connection resistance is unlikely to increase and conduction failure is unlikely to occur. Further, even if an impact is applied such as when the connection structure is dropped, the interface peeling between the conductive particles and the electrode can be suppressed.
  • the resin particles according to the present invention are used as a spacer (gap material) or an adhesive for electronic parts, the resin particles are satisfactorily deformed during thermocompression bonding between the resin particles and the member to be connected (adhesive body). Moreover, since the compressed shape is maintained even after thermocompression bonding, the contact area and frictional resistance between the resin particles and the member to be connected can be increased, and the resin particles can be easily fixed at a predetermined position. Therefore, the spacer or the adhesive for electronic parts using the resin particles according to the present invention can suppress the interfacial peeling between the resin particles and the member to be connected. In the spacer or the adhesive for electronic parts using the resin particles according to the present invention, the thickness between the members to be connected can be uniformly controlled.
  • the resin particles according to the present invention are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then released from compression at 25 ° C. in a direction orthogonal to the compression direction.
  • the coefficient of variation (CV value) of the aspect ratio of the resin particles after compression / release observed from is 10% or less.
  • the resin particles according to the present invention have different compression characteristics from the conventional resin particles.
  • a method of controlling the coefficient of variation (CV value) of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction to 10% or less for example, it has flexibility and low recoverability.
  • a method using resin particles can be mentioned.
  • Examples of the method for obtaining the resin particles having flexibility and low resilience include a method of lowering the reaction temperature at the time of producing the resin particles. More specifically, a method of using a thermosetting resin as a material for the resin particles and suppressing the reaction temperature to 80 ° C. or lower (preferably 70 ° C. or lower) can be mentioned.
  • the first plate and the second plate each have a flat surface.
  • a polyimide film having a thickness of 70% of the particle diameter of the resin particles is attached as a gap material to the end of the surface of the first plate or the second plate.
  • the first plate and the second plate are heated so that the surface temperature becomes 200 ° C.
  • Resin particles are placed on the surface of the heated first plate.
  • a vise heat press digital for example, "MNP2-002D" manufactured by AS ONE Corporation
  • the resin particles are compressed in the flat portions of the first plate and the second plate.
  • the compression conditions are a compression speed of 2000 mN / sec and a load of 20000 mN. With the resin particles compressed by 30%, the resin particles are held at 200 ° C. for 10 minutes under a load of 20000 mN, and then the compression is released. After the resin particles after compression and release are left at 25 ° C. for 1 hour under windless conditions, the resin particles are photographed with an electron microscope or an optical microscope, and the shape of the resin particles is observed.
  • the material of the first plate and the second plate is preferably glass, stainless steel (SUS), or silicon, and more preferably glass.
  • the particle size of the resin particles is preferably an average particle size, and preferably a number average particle size. The method for measuring the particle size of the resin particles will be described later.
  • the coefficient of variation (CV value) of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction is 10% or less. It is preferably 7% or less, more preferably 5% or less. It is preferable that the coefficient of variation of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction is small.
  • the coefficient of variation of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction may be 1% or more, or 3% or more.
  • the coefficient of variation (CV value) of the aspect ratio of the resin particles after compression and release observed from the direction orthogonal to the compression direction is obtained by observing 50 arbitrary resin particles with an electron microscope or an optical microscope and each resin particle. It is preferable to obtain the average value and standard deviation of the aspect ratios of.
  • CV value (%) ( ⁇ / Xn) ⁇ 100 ⁇ : Standard deviation of the aspect ratio of the resin particles after compression / release observed from a direction orthogonal to the compression direction
  • Xn Mean value of the aspect ratios of the resin particles after compression / release observed from a direction orthogonal to the compression direction
  • the resin particles may not be used by heating at 200 ° C., for example, and may not be used in a state of being compressed by 30%. Observation of the resin particles after compression and compression release of the resin particles is performed in order to evaluate the compression characteristics of the resin particles.
  • the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction generally exceeds 1.
  • the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction is preferably 1.1 or more, more preferably 1.3 or more, and preferably 5 or less. It is more preferably 3 or less, further preferably 2 or less, and particularly preferably 1.5 or less.
  • the aspect ratio is at least the above lower limit and at least the above upper limit, the contact area and frictional resistance between the resin particles or the particles using the resin particles and the member to be connected can be increased, and the resin particles or the resin particles are used. It becomes easier to fix the particles in place.
  • FIG. 1 is a cross-sectional view showing resin particles according to the first embodiment of the present invention.
  • FIG. 1A is a cross-sectional view showing the resin particles before compression
  • FIG. 1B is a cross-sectional view showing the resin particles after compression release.
  • 8 (a) shows a typical electron micrograph of the resin particles (resin particles before heat curing)
  • FIG. 8 (b) shows a typical electron micrograph of the resin particles after compression and release. Shown.
  • the shape of the resin particles 1 before compression shown in FIG. 1A is spherical.
  • the resin particles 1 after compression and release shown in FIG. 1 (b) are obtained by holding the resin particles 1 shown in FIG. 1 (a) at 200 ° C. for 10 minutes in a state of being compressed by 30% with respect to the particle size, and then from compression. These are the resin particles after compression release when released.
  • the compressed and released resin particles 1 shown in FIG. 1B have a first surface 1a (flat surface portion) and a second surface 1b (flat surface portion) facing each other in the compression direction P.
  • the first surface 1a and the second surface 1b are formed from the surfaces of the first plate and the second plate used during the 30% compression of the resin particles 1.
  • the first surface 1a and the second surface 1b are flat surfaces.
  • the shapes of the first surface 1a and the second surface 1b are circular, respectively.
  • A be the minor axis of the resin particles after compression release observed from the direction orthogonal to the compression direction.
  • B be the major axis of the resin particles after compression release observed from the direction orthogonal to the compression direction.
  • the aspect ratio of the resin particles after compression release is represented by B / A.
  • the minor axis (A) is preferably the diameter of the resin particles in the compression direction.
  • the major axis (B) is preferably the diameter of the resin particles in the direction orthogonal to the compression direction.
  • A is the distance between the first surface 1a and the second surface 1b.
  • B is the major axis of the resin particles 1 in the direction orthogonal to the compression direction P.
  • the resin particles after compression release do not have to have two flat portions facing each other in the compression direction.
  • the aspect ratio of the resin particles (before compression) is preferably 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less.
  • the aspect ratio of the resin particles (before compression) indicates a major axis / minor axis.
  • the aspect ratio of the resin particles (before compression) is such that 50 arbitrary resin particles are observed with an electron microscope or an optical microscope, the maximum diameter and the minimum diameter are set to the major axis and the minor axis, respectively, and the major axis / minor axis of each resin particle. It is preferable to obtain by calculating the average value of.
  • the particle size of the resin particles (before compression) can be appropriately set according to the application.
  • the particle size of the resin particles (before compression) is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, and particularly preferably 20 ⁇ m or less. Most preferably, it is 10 ⁇ m or less.
  • the particle diameter of the resin particles is not less than the above lower limit and not more than the above upper limit, the resin particles can be used more preferably depending on the use of the conductive particles and the spacer.
  • the particle size of the resin particles is preferably an average particle size, and preferably a number average particle size.
  • the particle size of the resin particles can be obtained, for example, by observing 50 arbitrary resin particles with an electron microscope or an optical microscope, calculating the average value of the particle size of each resin particle, or using a particle size distribution measuring device. Be done. In observation with an electron microscope or an optical microscope, the particle size of each resin particle is determined as the particle size in the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 resin particles in the circle equivalent diameter is substantially equal to the average particle diameter in the sphere equivalent diameter. In the particle size distribution measuring device, the particle size of each resin particle is obtained as the particle size in the equivalent diameter of a sphere.
  • the average particle size of the resin particles is preferably calculated using a particle size distribution measuring device.
  • the measurement can be performed as follows.
  • the coefficient of variation (CV value) of the particle size of the resin particles is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less.
  • the resin particles can be more preferably used depending on the use of the conductive particles and the spacer.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle size of resin particles Dn: Mean value of particle size of resin particles
  • the shape of the resin particles (before compression) is not particularly limited.
  • the shape of the resin particles (before compression) may be spherical, non-spherical, flat or the like.
  • the thermal decomposition temperature of the resin particles is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 350 ° C. or lower, and more preferably 300 ° C. or lower.
  • the thermal decomposition temperature of the resin particles is not less than the above lower limit and not more than the above upper limit, the shape of the resin particles after compression release can be improved, and the effect of the present invention can be more effectively exhibited. ..
  • the thermal decomposition temperature can be measured using a differential thermogravimetric simultaneous measuring device (for example, "TG / DTA: STA7200” manufactured by Hitachi High-Tech Science Co., Ltd.).
  • TG / DTA: STA7200 manufactured by Hitachi High-Tech Science Co., Ltd.
  • the temperature at which 10 mg of the resin particles is raised in air at 5 ° C./min and the weight in the measurement result is reduced by 10% is defined as the thermal decomposition temperature.
  • the compressive modulus (10% K value) when the resin particles are compressed by 10% is preferably 100 N / mm 2 or more, more preferably 500 N / mm 2 or more, still more preferably 1000 N / mm 2 or more, preferably 3500 N. / Mm 2 or less, more preferably 3200 N / mm 2 or less, still more preferably 2800 N / mm 2 or less.
  • the 10% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the compressive elastic modulus (30% K value) when the resin particles are compressed by 30% is preferably 100 N / mm 2 or more, more preferably 300 N / mm 2 or more, still more preferably 500 N / mm 2 or more, preferably 3000 N. / mm 2 or less, more preferably 2500N / mm 2, more preferably not more than 2000N / mm 2.
  • 30% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the compressive elastic modulus (10% K value and 30% K value) of the resin particles can be measured as follows.
  • the compressive elastic modulus (10% K value and 30% K value) can be calculated by the following formula.
  • the microcompression tester for example, "Fisherscope H-100" manufactured by Fisher Co., Ltd. is used.
  • the compressive elastic modulus (10% K value and 30% K value) of the resin particles is an arithmetic mean of the compressive elastic moduli (10% K value and 30% K value) of 50 arbitrarily selected resin particles. It is preferable to calculate by doing so.
  • the compressive elastic modulus universally and quantitatively represents the hardness of the resin particles. By using the compressive elastic modulus, the hardness of the resin particles can be expressed quantitatively and uniquely.
  • the compression recovery rate of the resin particles is preferably 5% or more, more preferably 8% or more, preferably 60% or less, and more preferably 40% or less.
  • the compression recovery rate is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the compression recovery rate of the resin particles can be measured as follows.
  • Compression recovery rate (%) [L2 / L1] x 100
  • L1 Compressive displacement from the origin load value when a load is applied to the reversing load value
  • L2 Unloading displacement from the reversing load value when the load is released to the origin load value
  • the use of the above resin particles is not particularly limited.
  • the resin particles are suitably used for various purposes. By changing the compression conditions of the resin particles at the time of use, the thickness of the resin particles can be suitably changed.
  • the resin particles are used for spacers, adhesives for electronic parts, for obtaining conductive particles having conductive portions, or for laminated modeling materials. It is more preferable that the resin particles are used as a spacer, an adhesive for electronic parts, or used to obtain conductive particles having a conductive portion. In the conductive particles, the conductive portion is formed on the surface of the resin particles.
  • the resin particles are preferably used as a spacer or as a spacer.
  • Examples of the method of using the spacer include a spacer for a liquid crystal display element, a spacer for gap control, a spacer for stress relaxation, and a spacer for a dimming laminate.
  • the gap control spacer is used for gap control of laminated chips for ensuring standoff height and flatness, and for gap control of optical components for ensuring smoothness of glass surface and thickness of adhesive layer. Can be used.
  • the stress relaxation spacer can be used for stress relaxation of a sensor chip or the like, stress relaxation of a connecting portion connecting two members to be connected, and the like. Examples of the sensor chip include a semiconductor sensor chip and the like.
  • the resin particles are preferably used as a spacer for a liquid crystal display element or as a spacer for a liquid crystal display element, and preferably used as a peripheral sealant for a liquid crystal display element.
  • the resin particles are preferably used as a spacer for displaying a liquid crystal, used as an adhesive for an electronic component, or used for obtaining conductive particles having a conductive portion.
  • the resin particles preferably function as spacers. Since the resin particles have good compressive deformation characteristics, the resin particles can be arranged between substrates by using the resin particles as spacers, or a conductive portion is formed on the surface and used as conductive particles to electrically connect the electrodes.
  • Spacers or conductive particles are efficiently placed between the substrates or between the electrodes when they are used. Further, since the resin particles can suppress the aggregation and movement of the spacers, the connection failure and the display failure in the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles Is less likely to occur.
  • the resin particles are preferably used as an adhesive for electronic parts or as an adhesive for electronic parts.
  • the adhesive for electronic components include an adhesive for liquid crystal panels, an adhesive for laminated substrates, an adhesive for substrate circuits, and an adhesive for camera modules.
  • the laminated substrate include a semiconductor sensor chip and the like.
  • the resin particles used in the adhesive for electronic parts or the resin particles used as the adhesive for electronic parts are preferably adhesive resin particles having adhesive performance. When the resin particles are adhesive resin particles, the resin particles and the member to be laminated can be satisfactorily adhered to each other when the resin particles are cured by pressure bonding.
  • the resin particles can be used alone as an adhesive for electronic parts.
  • the resin particles can be used as an adhesive for electronic components without using other adhesive components.
  • the resin particles When the resin particles are used as an adhesive for electronic parts, they may not be used alone as an adhesive for electronic parts, or may be used together with other adhesive components. Further, when the resin particles are adhesive resin particles having adhesive performance, they can also be used as a spacer and an adhesive for electronic parts.
  • the above resin particles are used as a spacer and an adhesive for electronic parts, the physical properties required for the spacer such as gap controllability and stress relaxation property are as compared with the case where the spacer and the adhesive are made of different materials. It is possible to achieve a higher degree of compatibility with adhesiveness.
  • the resin particles are preferably used as a material for laminated modeling.
  • a three-dimensional model can be formed by three-dimensionally laminating the resin particles to form a specific shape and then curing the resin particles.
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”
  • (meth) acrylic means one or both of “acrylic” and “methacrylic”. means.
  • the material of the resin particles is not particularly limited.
  • the material of the resin particles is preferably an organic material.
  • the resin particles may be particles having a porous structure or particles having a solid structure.
  • the porous structure means a structure having a plurality of pores.
  • the solid structure means a structure having no plurality of pores.
  • organic material examples include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene; acrylic resins such as polymethylmethacrylate and polymethylacrylate; polycarbonate, polyamide, phenolformaldehyde resin and melamine.
  • polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene
  • acrylic resins such as polymethylmethacrylate and polymethylacrylate
  • polycarbonate polyamide, phenolformaldehyde resin and melamine.
  • Formaldehyde resin benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, urethane resin, isocyanate resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal , Polystyrene, Polypropyleneimide, Polyether Ether Ketone, Polyethersulfone, Divinylbenzene Polymer, Divinylbenzene Copolymer and the like.
  • the divinylbenzene copolymer and the like include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylic acid ester copolymer.
  • the material of the resin particles is an epoxy resin, a melamine resin, a benzoguanamine resin, a urethane resin, an isocyanate resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a phenol resin, or a polymerizable monomer having an ethylenically unsaturated group. It is preferably a seed or a polymer obtained by polymerizing two or more kinds.
  • the material of the resin particles is one or more polymerized epoxy resin, melamine resin, benzoguanamine resin, polyimide resin, polyamide resin, polyamideimide resin, phenol resin, or polymerizable monomer having an ethylenically unsaturated group.
  • the material of the resin particles contains a thermosetting resin.
  • the thermosetting resin include epoxy resin, melamine resin, urethane resin, polyimide resin, phenol resin and the like, but other thermosetting resins may be used.
  • the material of the resin particles is particularly preferably an epoxy resin. When the material of the resin particles satisfies the above-mentioned preferable aspects, the compression characteristics of the resin particles can be more easily controlled in a suitable range.
  • the epoxy resin is preferably a polyfunctional epoxy resin.
  • the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, trifunctional epoxy resins such as triazine type epoxy resin and glycidylamine type epoxy resin, and tetrakisphenol ethane type epoxy. Examples thereof include resins and tetrafunctional epoxy resins such as glycidylamine type epoxy resins. Only one type of the epoxy resin may be used, or two or more types may be used in combination.
  • the curing agent heat-cures the epoxy resin.
  • the curing agent is not particularly limited. Examples of the curing agent include thiol curing agents such as imidazole curing agents, amine curing agents, phenol curing agents, and polythiol curing agents, and acid anhydride curing agents. Only one type of the thermosetting agent may be used, or two or more types may be used in combination. From the viewpoint of easily controlling the compression characteristics of the resin particles within a suitable range, the curing agent is preferably an amine curing agent.
  • the above imidazole curing agent is not particularly limited.
  • Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimerite, and 2,4-diamino-6.
  • the above thiol curing agent is not particularly limited.
  • examples of the thiol curing agent include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.
  • the above amine curing agent is not particularly limited.
  • examples of the amine curing agent include ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane and bis.
  • the amine curing agent is ethylenediamine, hexamethylenediamine, octamethylenediamine, metaphenylenediamine, diaminodiphenylsulfone, phenylenediamine, or 2,2.
  • -Bis [4- (4-aminophenoxy) phenyl] propane is preferred.
  • the amine curing agent is ethylenediamine, norbornanediamine, diaminodiphenylmethane, phenylenediamine, or 2,2-bis [4- (4-aminophenoxy). ) Phenyl] Propane is more preferred.
  • the above-mentioned acid anhydride curing agent is not particularly limited, and any acid anhydride used as a curing agent for a thermosetting compound such as an epoxy compound can be widely used.
  • the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylbutenyltetrahydrophthalic anhydride.
  • Bifunctional such as phthalic acid derivative anhydride, maleic anhydride, nadic acid anhydride, methylnadic anhydride, glutaric anhydride, succinic anhydride, glycerinbis trimellitic anhydride monoacetate, and ethylene glycolbis trimellitic anhydride.
  • Acid anhydride curing agent trifunctional acid anhydride curing agent such as trimellitic anhydride, and pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, polyazelineic acid anhydride, etc. Examples thereof include an acid anhydride curing agent having four or more functions.
  • the polymerizable monomer having an ethylenically unsaturated group is a non-crosslinkable monomer.
  • examples thereof include crosslinkable monomers.
  • non-crosslinkable monomer examples include styrene monomers such as styrene, ⁇ -methylstyrene and chlorostyrene; vinyl ether compounds such as methylvinyl ether, ethylvinyl ether and propylvinyl ether; vinyl acetate, vinyl butyrate, etc.
  • Acid vinyl ester compounds such as vinyl laurate and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; as (meth) acrylic compounds, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and other alkyl ( Meta) acrylate compound; oxygen atom-containing (meth) acrylate compound such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate; (meth)
  • Nitrile-containing monomer Halogen-containing (meth) acrylate compound such as trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate; olefins such as diisobutylene, isobutylene, linearene, ethylene and propylene as ⁇ -olefin compounds Compound;
  • Examples of the conjugated diene compound include isoprene and butadiene.
  • crosslinkable monomer examples include vinyl monomers such as divinylbenzene, 1,4-dibinyloxybutane, and divinylsulfone as vinyl compounds; and tetramethylolmethanetetra (meth) acrylate as (meth) acrylic compounds.
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group.
  • the above-mentioned polymerization method is not particularly limited, and examples thereof include known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, polycondensation polymerization), addition condensation, living polymerization, and living radical polymerization. Further, as another polymerization method, suspension polymerization in the presence of a radical polymerization initiator can be mentioned.
  • the conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • the conductive particles 11 shown in FIG. 2 have a resin particle 1 and a conductive portion 2 arranged on the surface of the resin particle 1.
  • the conductive portion 2 covers the surface of the resin particles 1.
  • the conductive particles 11 are coated particles in which the surface of the resin particles 1 is coated with the conductive portion 2.
  • FIG. 3 is a cross-sectional view showing the conductive particles according to the second embodiment of the present invention.
  • the conductive particles 21 shown in FIG. 3 have a resin particle 1 and a conductive portion 22 arranged on the surface of the resin particle 1. In the conductive particles 21 shown in FIG. 3, only the conductive portion 22 is different from the conductive particles 11 shown in FIG.
  • the conductive portion 22 has a first conductive portion 22A which is an inner layer and a second conductive portion 22B which is an outer layer.
  • the first conductive portion 22A is arranged on the surface of the resin particles 1.
  • the second conductive portion 22B is arranged on the surface of the first conductive portion 22A.
  • FIG. 4 is a cross-sectional view showing the conductive particles according to the third embodiment of the present invention.
  • the conductive particle 31 shown in FIG. 4 has a resin particle 1, a conductive portion 32, a plurality of core substances 33, and a plurality of insulating substances 34.
  • the conductive portion 32 is arranged on the surface of the resin particles 1.
  • the conductive particles 31 have a plurality of protrusions 31a on the conductive surface.
  • the conductive portion 32 has a plurality of protrusions 32a on the outer surface.
  • the conductive particles may have protrusions on the conductive surface of the conductive particles, or may have protrusions on the outer surface of the conductive portion.
  • a plurality of core substances 33 are arranged on the surface of the resin particles 1.
  • the plurality of core substances 33 are embedded in the conductive portion 32.
  • the core material 33 is arranged inside the protrusions 31a and 32a.
  • the conductive portion 32 covers a plurality of core substances 33.
  • the outer surface of the conductive portion 32 is raised by the plurality of core substances 33, and protrusions 31a and 32a are formed.
  • the conductive particles 31 have an insulating substance 34 arranged on the outer surface of the conductive portion 32. At least a part of the outer surface of the conductive portion 32 is covered with the insulating substance 34.
  • the insulating substance 34 is formed of an insulating material and is an insulating particle. As described above, the conductive particles may have an insulating substance arranged on the outer surface of the conductive portion.
  • the metal for forming the conductive portion is not particularly limited.
  • the metals include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, tarium, germanium, cadmium, silicon, tungsten and molybdenum. And these alloys and the like.
  • the metal include tin-doped indium oxide (ITO) and solder. From the viewpoint of further enhancing the connection reliability between the electrodes, the metal is preferably a tin-containing alloy, nickel, palladium, copper or gold, and preferably nickel or palladium.
  • the conductive portion may be formed of one layer, such as the conductive particles 11 and 31. Like the conductive particles 21, the conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers.
  • the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer or an alloy layer containing tin and silver, and is preferably a gold layer. Is more preferable.
  • the outermost layer is these preferable conductive portions, the connection reliability between the electrodes can be further enhanced. Further, when the outermost layer is a gold layer, the corrosion resistance can be further improved.
  • the method of forming the conductive portion on the surface of the resin particles is not particularly limited.
  • Examples of the method for forming the conductive portion include a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating a metal powder or a paste containing a metal powder and a binder on the surface of resin particles. Can be mentioned. From the viewpoint of forming the conductive portion more easily, the method by electroless plating is preferable.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
  • 10% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • 30% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the compressive elastic modulus (10% K value and 30% K value) of the conductive particles can be measured in the same manner as the compressive elastic modulus (10% K value and 30% K value) of the resin particles.
  • the compressive elastic modulus universally and quantitatively represents the hardness of conductive particles. By using the compressive elastic modulus, the hardness of the conductive particles can be expressed quantitatively and uniquely.
  • the compression recovery rate of the conductive particles is preferably 5% or more, more preferably 8% or more, preferably 60% or less, and more preferably 40% or less.
  • the compression recovery rate is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
  • the compression recovery rate of the conductive particles can be measured in the same manner as the compression recovery rate of the resin particles.
  • the particle size of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less. Especially preferably, it is 20 ⁇ m or less.
  • the particle diameter of the conductive particles is equal to or greater than the above lower limit and equal to or less than the above upper limit, the contact area between the conductive particles and the electrodes becomes sufficiently large when the electrodes are connected using the conductive particles, and the conductivity is increased. It becomes difficult to form agglomerated conductive particles when forming the portion.
  • the distance between the electrodes connected via the conductive particles does not become too large, and the conductive portion does not easily peel off from the surface of the resin particles.
  • the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of the conductive material.
  • the particle diameter of the conductive particles means the diameter when the conductive particles are spherical, and when the conductive particles have a shape other than spherical, it is assumed to be a true sphere corresponding to the volume. Means the diameter of.
  • the particle size of the conductive particles is preferably an average particle size, and more preferably a number average particle size.
  • the particle size of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or performing a laser diffraction type particle size distribution measurement. In observation with an electron microscope or an optical microscope, the particle size of each conductive particle is determined as the particle size in the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 conductive particles in the circle equivalent diameter is substantially equal to the average particle diameter in the sphere equivalent diameter. In the laser diffraction type particle size distribution measurement, the particle size of each conductive particle is determined as the particle size in the equivalent sphere diameter.
  • the particle size of the conductive particles is preferably calculated by laser diffraction type particle size distribution measurement.
  • the thickness of the conductive portion is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 0.3 ⁇ m or less.
  • the thickness of the conductive portion is the thickness of the entire conductive portion when the conductive portion has multiple layers. When the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not too hard and the conductive particles are sufficiently deformed at the time of connection between the electrodes. To do.
  • the thickness of the conductive portion of the outermost layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably. Is 0.1 ⁇ m or less.
  • the thickness of the conductive portion of the outermost layer is equal to or higher than the lower limit and lower than the upper limit, the coating by the conductive portion of the outermost layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection reliability between the electrodes becomes higher. It can be further enhanced. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.
  • the thickness of the conductive portion can be measured by observing the cross section of the conductive particles, for example, using a transmission electron microscope (TEM). Regarding the thickness of the conductive portion, it is preferable to calculate the average value of the thickness of any of the conductive portions at five points as the thickness of the conductive portion of one conductive particle, and the average value of the thickness of the entire conductive portion is one. It is more preferable to calculate as the thickness of the conductive portion of the conductive particles. The thickness of the conductive portion is preferably obtained by calculating the average value of the thickness of the conductive portion of each conductive particle for 50 arbitrary conductive particles.
  • TEM transmission electron microscope
  • the conductive particles have protrusions on the outer surface of the conductive portion.
  • the conductive particles preferably have protrusions on the conductive surface. It is preferable that the number of the protrusions is plurality.
  • An oxide film is often formed on the surface of the conductive portion and the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively removed by the protrusions by arranging the conductive particles between the electrodes and crimping them. Therefore, the electrodes and the conductive portions of the conductive particles can be brought into contact with each other more reliably, and the connection resistance between the electrodes can be further reduced.
  • the conductive particles have an insulating substance on the surface, or when the conductive particles are dispersed in the binder resin and used as a conductive material, the protrusions of the conductive particles cause the conductive particles to be connected to the electrode.
  • the insulating substance or binder resin between them can be eliminated more effectively. Therefore, the connection reliability between the electrodes can be further improved.
  • a method of forming protrusions on the surface of the conductive particles As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive portion by electroless plating after adhering a core material to the surface of the resin particles, and a method of forming a conductive portion on the surface of the resin particles by electroless plating. Examples thereof include a method in which a core material is attached after forming the portion, and then a conductive portion is formed by electroless plating. Further, it is not necessary to use the core substance in order to form the protrusions.
  • Examples of the method for forming the protrusions include the following methods.
  • metal nuclei are generated by electroless plating, metal nuclei are attached to the surface of resin particles or conductive parts, and the conductive parts are further formed by electroless plating. how to.
  • the conductive particles further include an insulating substance arranged on the outer surface of the conductive portion.
  • an insulating substance arranged on the outer surface of the conductive portion.
  • the insulating substance is preferably an insulating resin layer or insulating particles, and more preferably insulating particles.
  • the insulating particles are preferably insulating resin particles.
  • the outer surface of the conductive portion and the surface of the insulating particles may each be coated with a compound having a reactive functional group.
  • the outer surface of the conductive portion and the surface of the insulating particles may not be directly chemically bonded, or may be indirectly chemically bonded by a compound having a reactive functional group.
  • the carboxyl group may be chemically bonded to a functional group on the surface of the insulating particles via a polymer electrolyte such as polyethyleneimine.
  • the conductive material includes the above-mentioned conductive particles and a binder resin.
  • the conductive particles are preferably dispersed in the binder resin and used as a conductive material.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection of electrodes.
  • the conductive material is preferably a circuit connection material.
  • the binder resin is not particularly limited.
  • the binder resin a known insulating resin is used.
  • the binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component.
  • the curable component include a photocurable component and a thermosetting component.
  • the photocurable component preferably contains a photocurable compound and a photopolymerization initiator.
  • the thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
  • the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. Only one kind of the binder resin may be used, or two or more kinds may be used in combination.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, styrene resin and the like.
  • the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins.
  • Examples of the curable resin include epoxy resin, urethane resin, polyimide resin, unsaturated polyester resin and the like.
  • the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
  • the curable resin may be used in combination with a curing agent.
  • thermoplastic block copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated additive of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene.
  • -Hydrogen additives for styrene block copolymers and the like can be mentioned.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the conductive material includes, for example, a filler, a bulking agent, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a photostabilizer. It may contain various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant.
  • the method for dispersing the conductive particles in the binder resin is not particularly limited as a conventionally known dispersion method can be used.
  • Examples of the method for dispersing the conductive particles in the binder resin include the following methods. A method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. A method in which the conductive particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, added to the binder resin, and kneaded and dispersed by a planetary mixer or the like. A method in which the binder resin is diluted with water, an organic solvent or the like, the conductive particles are added, and the binder resin is kneaded and dispersed with a planetary mixer or the like.
  • the viscosity ( ⁇ 25) of the conductive material at 25 ° C. is preferably 30 Pa ⁇ s or more, more preferably 50 Pa ⁇ s or more, preferably 400 Pa ⁇ s or less, and more preferably 300 Pa ⁇ s or less.
  • the viscosity ( ⁇ 25) can be appropriately adjusted depending on the type and amount of the compounding components.
  • the viscosity ( ⁇ 25) can be measured at 25 ° C. and 5 rpm using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.).
  • the conductive material can be used as a conductive paste, a conductive film, or the like.
  • the conductive material according to the present invention is a conductive film, a film containing no conductive particles may be laminated on the conductive film containing the conductive particles.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder resin in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more. Is 99.99% by weight or less, more preferably 99.9% by weight or less.
  • the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further improved.
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. % Or less, still more preferably 40% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less.
  • the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be further effectively lowered, and the connection reliability between the electrodes can be further effectively reduced. Can be enhanced.
  • connection structure can be obtained by connecting the members to be connected using the resin particles described above.
  • connection structure using the resin particles connects the first connection target member, the second connection target member, the first connection target member, and the second connection target member. It has a part.
  • the connection portion is formed of the resin particles or a composition containing the resin particles.
  • the resin particles are in direct contact with the first connection target member and the second connection target member.
  • a connection structure can be obtained by connecting the members to be connected using the above-mentioned conductive particles or a conductive material containing the above-mentioned conductive particles and a binder resin.
  • connection structure using the conductive particles includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, and the first connection. It includes a connecting portion that connects the target member and the second connection target member.
  • the connection portion is formed of conductive particles or is formed of a conductive material containing the conductive particles and a binder resin.
  • the conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles.
  • the first electrode and the second electrode are electrically connected by the conductive particles.
  • the connecting portion itself is a conductive particle. That is, the first connection target member and the second connection target member are connected by the conductive particles.
  • the conductive material used to obtain the connection structure is preferably an anisotropic conductive material.
  • FIG. 5 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention.
  • connection structure 41 shown in FIG. 5 is a connection connecting the first connection target member 42, the second connection target member 43, the first connection target member 42, and the second connection target member 43.
  • a unit 44 is provided.
  • the connecting portion 44 is formed of a conductive material containing the conductive particles 11 and the binder resin.
  • the conductive particles 11 are shown schematically. Instead of the conductive particles 11, other conductive particles 21 and 31 may be used.
  • the first connection target member 42 has a plurality of first electrodes 42a on the surface (upper surface).
  • the second connection target member 43 has a plurality of second electrodes 43a on the surface (lower surface).
  • the first electrode 42a and the second electrode 43a are electrically connected by one or more conductive particles 11. Therefore, the first and second connection target members 42 and 43 are electrically connected by the conductive particles 11.
  • connection structure is not particularly limited.
  • the conductive material is arranged between a first connection target member and a second connection target member, and after obtaining a laminate, the laminate is heated and pressurized.
  • the method and the like can be mentioned.
  • the pressure at the time of pressurization is preferably 40 MPa or more, more preferably 60 MPa or more, preferably 90 MPa or less, and more preferably 70 MPa or less.
  • the temperature at the time of heating is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 140 ° C. or lower, and more preferably 120 ° C. or lower.
  • the first connection target member and the second connection target member are not particularly limited.
  • Specific examples of the first connection target member and the second connection target member include electronic components such as semiconductor chips, semiconductor packages, LED chips, LED packages, capacitors and diodes, resin films, printed circuit boards, and flexible devices. Examples thereof include electronic components such as printed circuit boards, flexible flat cables, rigid flexible boards, glass epoxy boards, and circuit boards such as glass boards.
  • the first connection target member and the second connection target member are preferably electronic components.
  • the conductive material is preferably a conductive material for connecting electronic components.
  • the conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in the paste-like state.
  • connection target member is a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film.
  • the connection target member is preferably a flexible substrate, and is preferably a connection target member in which electrodes are arranged on the surface of the resin film.
  • the flexible substrate is a flexible printed circuit board or the like, the flexible substrate generally has electrodes on its surface.
  • the electrodes provided on the connection target member include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes, SUS electrodes, and tungsten electrodes.
  • the electrodes are preferably gold electrodes, nickel electrodes, tin electrodes, silver electrodes or copper electrodes.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
  • the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer.
  • the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al and Ga.
  • the resin particles can be suitably used as a spacer for a liquid crystal display element.
  • the first connection target member may be a first liquid crystal display element member.
  • the second connection target member may be a second liquid crystal display element member.
  • the first liquid crystal display element member and the second liquid crystal display element member are in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other. It may be a sealing portion that seals the outer periphery of and.
  • the resin particles can also be used as a peripheral sealant for a liquid crystal display element.
  • the liquid crystal display element includes a first liquid crystal display element member and a second liquid crystal display element member.
  • the first liquid crystal display element member and the second liquid crystal display element member are in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other.
  • a seal portion that seals the outer periphery of the liquid crystal, and a liquid crystal that is arranged inside the seal portion between the first liquid crystal display element member and the second liquid crystal display element member. Be prepared.
  • the liquid crystal dropping method is applied, and the sealing portion is formed by thermosetting the sealing agent for the liquid crystal dropping method.
  • the arrangement density of the spacers for the liquid crystal display element per 1 mm 2 is preferably 10 pieces / mm 2 or more, and preferably 1000 pieces / mm 2 or less.
  • the arrangement density is 10 pieces / mm 2 or more, the cell gap becomes even more uniform.
  • the arrangement density is 1000 pieces / mm 2 or less, the contrast of the liquid crystal display element becomes even better.
  • the resin particles or conductive particles described above are arranged between the first ceramic member and the second ceramic member at the outer peripheral portion of the first ceramic member and the second ceramic member, and are a gap control material and a conductive material. It can also be used as a connecting material.
  • FIG. 6 is a cross-sectional view showing an example of an electronic component device using the resin particles according to the present invention.
  • FIG. 7 is an enlarged cross-sectional view showing a joint portion in the electronic component device shown in FIG.
  • the electronic component device 81 shown in FIGS. 6 and 7 includes a first ceramic member 82, a second ceramic member 83, a joint portion 84, an electronic component 85, and a lead frame 86.
  • the first and second ceramic members 82 and 83 are each made of a ceramic material.
  • the first and second ceramic members 82 and 83 are, for example, housings, respectively.
  • the first ceramic member 82 is, for example, a substrate.
  • the second ceramic member 83 is, for example, a lid.
  • the first ceramic member 82 has a convex portion protruding toward the second ceramic member 83 side (upper side) on the outer peripheral portion.
  • the first ceramic member 82 has a recess on the second ceramic member 83 side (upper side) that forms an internal space R for accommodating the electronic component 85.
  • the first ceramic member 82 does not have to have a convex portion.
  • the second ceramic member 83 has a convex portion protruding toward the first ceramic member 82 side (lower side) on the outer peripheral portion.
  • the second ceramic member 83 has a recess on the first ceramic member 82 side (lower side) that forms an internal space R for accommodating the electronic component 85.
  • the second ceramic member 83 does not have to have a convex portion.
  • the internal space R is formed by the first ceramic member 82 and the second ceramic member 83.
  • the joint portion 84 joins the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83. Specifically, the joint portion 84 joins the convex portion of the outer peripheral portion of the first ceramic member 82 and the convex portion of the outer peripheral portion of the second ceramic member 83.
  • the package is formed by the first and second ceramic members 82 and 83 joined by the joint portion 84.
  • the internal space R is formed by the package.
  • the joint portion 84 seals the internal space R in a liquid-tight and airtight manner.
  • the joint portion 84 is a sealing portion.
  • the electronic component 85 is arranged in the internal space R of the above package. Specifically, the electronic component 85 is arranged on the first ceramic member 82. In this embodiment, two electronic components 85 are used.
  • the joint portion 84 includes a plurality of resin particles 1 and glass 84B.
  • the bonding portion 84 is formed by using a bonding material containing a plurality of resin particles 1 different from the glass particles and the glass 84B.
  • This bonding material is a bonding material for ceramic packages.
  • the bonding material may contain the above-mentioned conductive particles instead of the above-mentioned resin particles.
  • the bonding material may contain a solvent or a resin.
  • glass 84B such as glass particles is melted and bonded and then solidified.
  • Examples of electronic components include sensor elements, MEMS, bare chips, and the like.
  • Examples of the sensor element include a pressure sensor element, an acceleration sensor element, a CMOS sensor element, a CCD sensor element, and a housing of the various sensor elements.
  • the lead frame 86 is arranged between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83.
  • the lead frame 86 extends to the internal space R side and the external space side of the package.
  • the terminal of the electronic component 85 and the lead frame 86 are electrically connected via a wire.
  • the joint portion 84 partially directly joins the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83, and partially indirectly joins them.
  • the joint portion 84 is the outer peripheral portion of the first ceramic member 82 at the portion where the lead frame 86 is located between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83.
  • the outer peripheral portion of the second ceramic member 83 are indirectly joined via the lead frame 86.
  • the first ceramic member 82 is in contact with the lead frame 86
  • the lead frame 86 is in contact with the lead frame 86.
  • the joint portion 84 is a portion between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83 where there is no lead frame 86, and the outer peripheral portion of the first ceramic member 82 and the second ceramic It is directly joined to the outer peripheral portion of the member 83.
  • the joint portion 84 is formed with the first ceramic member 82 and the second ceramic member 83. Is in contact with.
  • the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83 In the portion where the lead frame 86 is located between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83, the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83.
  • the distance between the two and the ceramic particles 1 is controlled by a plurality of resin particles 1 contained in the joint portion 84.
  • the joint portion may be a direct or indirect joint between the outer peripheral portion of the first ceramic member and the outer peripheral portion of the second ceramic member.
  • An electrical connection method other than the lead frame may be adopted.
  • the electronic component device includes, for example, a first ceramic member formed of a ceramic material, a second ceramic member formed of a ceramic material, a joint portion, and an electronic component. May be provided.
  • the joint portion may directly or indirectly join the outer peripheral portion of the first ceramic member and the outer peripheral portion of the second ceramic member.
  • the package may be formed by the first and second ceramic members joined by the joining portion.
  • the electronic component is arranged in the internal space of the package, and the joint may include a plurality of resin particles and glass.
  • the ceramic package bonding material is used in the electronic component device to form the bonding portion, and includes resin particles and glass.
  • An electrical connection method containing only resin particles and not glass may be adopted.
  • the joint portion may contain the above-mentioned conductive particles instead of the above-mentioned resin particles.
  • Example 1 (1) Preparation of resin particles In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 15 parts by weight of bisphenol A type epoxy resin (“EXA-850-CRP” manufactured by DIC) and polyvinylpyrrolidone as a dispersion stabilizer. 7.5 parts by weight and 250 parts by weight of ethanol were added, and the mixture was uniformly dissolved by stirring at 68 ° C. for 1 hour. Next, 4.25 parts by weight of 4,4'-diaminodiphenylmethane and 35 parts by weight of ethanol were added and dissolved uniformly, then added into a reaction vessel and reacted at 68 ° C. for 20 hours. , The reaction product was obtained. The obtained reaction product was washed and dried to obtain resin particles.
  • EXA-850-CRP manufactured by DIC
  • polyvinylpyrrolidone as a dispersion stabilizer.
  • 7.5 parts by weight and 250 parts by weight of ethanol were added, and the
  • a nickel plating solution (pH 8.5) containing nickel sulfate 0.35 mol / L, dimethylamine borane 1.38 mol / L and sodium citrate 0.5 mol / L was prepared.
  • the nickel plating solution was gradually added dropwise to the dispersion to perform electroless nickel plating. Then, the dispersion liquid was filtered to take out the particles, washed with water, and dried to form a nickel-boron conductive layer on the surface of the resin particles to obtain conductive particles having a conductive portion on the surface.
  • Conductive Material (Anisically Conductive Paste) 7 parts by weight of the obtained conductive particles, 25 parts by weight of bisphenol A type phenoxy resin, 4 parts by weight of fluorene type epoxy resin, and 30 parts by weight of phenol novolac type epoxy resin.
  • a conductive material anisotropic conductive paste
  • SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.
  • connection target in which an IZO electrode pattern (first electrode, Vickers hardness of metal on the electrode surface 100 Hv) having an L / S of 10 ⁇ m / 10 ⁇ m is formed on the upper surface.
  • IZO electrode pattern first electrode, Vickers hardness of metal on the electrode surface 100 Hv
  • second connection target member having an Au electrode pattern (second electrode, Vickers hardness of metal on the electrode surface 50 Hv) having an L / S of 10 ⁇ m / 10 ⁇ m formed on the lower surface was prepared.
  • anisotropic conductive paste was coated on the transparent glass substrate so as to have a thickness of 30 ⁇ m to form an anisotropic conductive paste layer.
  • the semiconductor chips were laminated on the anisotropic conductive paste layer so that the electrodes face each other. After that, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100 ° C., the pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 55 MPa is applied to form the anisotropic conductive paste layer. It was cured at 100 ° C. to obtain a connection structure.
  • Example 2 In the production of the resin particles, a glycidylamine type epoxy resin (“TETRAD-X” manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of the bisphenol A type epoxy resin, and isopropyl alcohol was used instead of ethanol. Moreover, the compounding amount of 4,4'-diaminodiphenylmethane at the time of producing the resin particles was changed to 7.53 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • TTRAD-X glycidylamine type epoxy resin
  • isopropyl alcohol was used instead of ethanol.
  • the compounding amount of 4,4'-diaminodiphenylmethane at the time of producing the resin particles was changed to 7.53 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • Example 3 When producing the resin particles, a triazine type epoxy resin (“TEPIC-PAS” manufactured by Nissan Chemical Industries, Ltd.) was used instead of the bisphenol A type epoxy resin. Further, when producing the resin particles, 1.63 parts by weight of ethylenediamine was used instead of 4.25 parts by weight of 4,4′-diaminodiphenylmethane. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • TPIC-PAS triazine type epoxy resin
  • Example 4 When producing the resin particles, a glycidylamine type epoxy resin (“JER-630” manufactured by Mitsubishi Chemical Corporation) was used instead of the bisphenol A type epoxy resin. In addition, the amount of 4,4'-diaminodiphenylmethane blended in the preparation of the resin particles was changed to 7.63 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • Example 5 When producing the resin particles, an alicyclic glycidylamine type epoxy resin (“TETRAD-C” manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of the bisphenol A type epoxy resin, and isopropyl alcohol was used instead of ethanol. In addition, the blending amount of 4,4'-diaminodiphenylmethane at the time of producing the resin particles was changed to 7.44 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • TTRAD-C alicyclic glycidylamine type epoxy resin
  • isopropyl alcohol was used instead of ethanol.
  • the blending amount of 4,4'-diaminodiphenylmethane at the time of producing the resin particles was changed to 7.44 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • Example 6 Resin particles were obtained in the same manner as in Example 1. At the time of producing the conductive particles, 1 g of nickel particle slurry (average particle diameter 100 nm) was added to the dispersion liquid over 3 minutes to obtain a suspension containing the resin particles to which the core substance was attached. Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the suspension was used instead of the dispersion.
  • Example 7 (1) Preparation of Insulating Particles After putting the following monomer composition in a 1000 mL separable flask equipped with a four-mouth separable cover, a stirring blade, a three-way cock, a cooling tube and a temperature probe, the following monomer composition Distilled water was added so that the solid content was 10% by weight, the mixture was stirred at 200 rpm, and polymerization was carried out at 60 ° C. for 24 hours under a nitrogen atmosphere.
  • the monomer composition comprises 360 mmol of methyl methacrylate, 45 mmol of glycidyl methacrylate, 20 mmol of parastyryldiethylphosphine, 13 mmol of ethylene glycol dimethacrylate, 0.5 mmol of polyvinylpyrrolidone, and 2,2'-azobis ⁇ 2- [N- (2). -Carboxyethyl) amidino] propane ⁇ 1 mmol. After completion of the reaction, freeze-drying was performed to obtain insulating particles (particle diameter 360 nm) having a phosphorus atom derived from parastilyl diethylphosphine on the surface.
  • Example 6 (2) Preparation of Conductive Particles with Insulating Particles
  • the conductive particles obtained in Example 6 were prepared.
  • the insulating particles obtained above were dispersed in distilled water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of the insulating particles.
  • 10 g of the prepared conductive particles were dispersed in 500 mL of distilled water, 1 g of a 10 wt% aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 8 hours. After filtering with a 3 ⁇ m mesh filter, the mixture was further washed with methanol and dried to obtain conductive particles with insulating particles.
  • a conductive material and a connecting structure were obtained in the same manner as in Example 1 except that the conductive particles with insulating particles were used instead of the conductive particles.
  • Example 8 Polystyrene particles having an average particle diameter of 0.93 ⁇ m were prepared as seed particles.
  • a mixed solution was prepared by mixing 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol. After the above mixed solution was dispersed by ultrasonic waves, it was placed in a separable flask and stirred uniformly.
  • the emulsion was added to the mixture in the separable flask in several portions and stirred for 12 hours to allow the seed particles to absorb the monomer to obtain a suspension containing the seed particles in which the monomer was swollen. ..
  • Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the obtained resin particles were used.
  • Example 9 In the preparation of the resin particles, 2.34 parts by weight of 1,4-phenylenediamine was used instead of 4.25 parts by weight of 4,4'-diaminodiphenylmethane. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • Example 10 In the preparation of the resin particles, 8.90 parts by weight of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was used instead of 4.25 parts by weight of 4,4'-diaminodiphenylmethane. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
  • Polystyrene particles having an average particle diameter of 0.93 ⁇ m were prepared as seed particles.
  • a mixed solution was prepared by mixing 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol. After the above mixed solution was dispersed by ultrasonic waves, it was placed in a separable flask and stirred uniformly.
  • the emulsion was added to the mixture in the separable flask in several portions and stirred for 12 hours to allow the seed particles to absorb the monomer to obtain a suspension containing the seed particles in which the monomer was swollen. ..
  • Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the obtained resin particles were used.
  • Comparative Example 2 Conductive particles, conductive materials, and connections in the same manner as in Comparative Example 1, except that 30 parts by weight of 1,6-hexanediol dimethacrylate and 120 parts by weight of styrene were used instead of 150 parts by weight of divinylbenzene. Obtained a structure.
  • Comparative Example 3 As the resin particles, “Optobeads 3500M” manufactured by Nissan Chemical Industries, Ltd. was prepared. Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the prepared resin particles were used.
  • Particle diameter of resin particles (number average particle diameter) With respect to the obtained resin particles, the particle diameters of about 100,000 resin particles were measured using a particle size distribution measuring device (“Multisizer 4” manufactured by Beckman Coulter), and an average value was calculated.
  • a first plate and a second plate whose material is glass were prepared.
  • the first plate and the second plate each have a flat surface.
  • a polyimide film having a thickness of 70% of the particle diameter of the resin particles was attached to the end of the surface of the first plate as a gap material. After heating so that the surface temperature of the first plate and the second plate became 200 ° C., the obtained resin particles were arranged on the surface of the heated first plate. Within 3 to 5 minutes after arranging the resin particles, the distance between the first plate and the second plate was reduced using a vise heat press digital (“MNP2-002D” manufactured by AS ONE Corporation).
  • MNP2-002D vise heat press digital
  • the first plate or the second plate was moved to a position where it became 70% of the particle diameter (number average particle diameter) of the resin particles. That is, the resin particles were compressed by 30% with respect to the particle size (number average particle size).
  • the compression conditions were a compression speed of 2000 mN / sec and a load of 20000 mN.
  • the resin particles were held at 200 ° C. for 10 minutes under a load of 20000 mN in a state of being compressed by 30%, and then the compression was released.
  • the resin particles after compression release were left at 25 ° C. for 1 hour under windless conditions, and then the resin particles were photographed with an electron microscope.
  • the thermal decomposition temperature of the obtained resin particles was measured using a differential thermal thermal weight simultaneous measuring device (“TG / DTA: STA7200” manufactured by Hitachi High-Tech Science Co., Ltd.).
  • the thermal decomposition temperature is the temperature at which 10 mg of the resin particles are heated in air at 5 ° C./min and the weight in the measurement result is reduced by 10%.
  • Thickness of Conductive Part The obtained conductive particles were added to "Technobit 4000” manufactured by Kulzer and dispersed so as to have a content of 30% by weight to prepare an embedded resin body for inspection. A cross section of the conductive particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the embedded resin body for inspection.
  • IM4000 manufactured by Hitachi High-Technologies Corporation
  • FE-TEM field emission transmission electron microscope
  • connection structure Adhesion between Resin Particles and Conductive Part
  • the conductive particles in the connection part were observed using a scanning electron microscope (“Regulus 8220” manufactured by Hitachi High-Technologies Corporation). With respect to the 100 conductive particles observed, it was confirmed whether or not the conductive portion arranged on the surface of the resin particles was peeled off. The adhesion between the resin particles and the conductive portion was judged according to the following criteria.
  • connection structure With respect to the obtained connection structure, the conductive particles in the connection portion were observed using a scanning electron microscope (“Regulus 8220” manufactured by Hitachi High-Technologies Corporation). It was confirmed whether or not the compressed shape of the 100 conductive particles observed was maintained. The shape-maintaining characteristics of the conductive particles were judged according to the following criteria.
  • ⁇ ⁇ ⁇ The number of conductive particles maintaining the compressed shape is 90 or more ⁇ ⁇ : The number of conductive particles maintaining the compressed shape is 70 or more and less than 90 ⁇ : Compressed The number of conductive particles maintaining the shape is 50 or more and less than 70 ⁇ : The number of conductive particles maintaining the compressed shape is 1 or more and less than 50 ⁇ : The conductive particles are compressed The shape is not maintained or the conductive particles are destroyed.
  • connection reliability between the upper and lower electrodes
  • the connection resistance between the upper and lower electrodes of the 20 obtained connection structures was measured by the 4-terminal method, respectively.
  • connection reliability after high temperature and high humidity conditions The obtained 100 connection structures were left at 85 ° C. and 85% RH for 100 hours. For 100 connection structures after being left to stand, it was evaluated whether or not there was a conduction failure between the upper and lower electrodes. The connection reliability after high temperature and high humidity conditions was judged according to the following criteria.
  • ⁇ Of the 100 connection structures, the number of poor continuity is 1 or less. ⁇ : Of the 100 connection structures, the number of poor continuity is 2 or more and 5 or less. ⁇ : 6 or more and 10 or less of the 100 connection structures have poor continuity. ⁇ : 11 or more of the 100 connection structures have poor continuity.
  • FIG. 9 is an electron micrograph of the resin particles after compression release in Example 8.
  • FIG. 10 (a) is an electron micrograph of the resin particles after compression and release in Comparative Example 1
  • FIG. 10 (b) is an electron micrograph of the resin particles after compression and release in Comparative Example 2.
  • FIG. (C) is an electron micrograph of the resin particles after compression and release in Comparative Example 3.

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Abstract

Provided is a resin particle whereby it becomes possible to increase the contact area and the friction resistance between the resin particle or a particle comprising the resin particle and an object of interest and therefore it becomes possible to prevent the occurrence of interfacial peeling between the resin particle or the particle comprising the resin particle and the object of interest.　The resin particle according to the present invention has such a property that, when the resin particle is retained at 200°C for 10 minutes while compressing the resin particle by 30% relative to the particle diameter of the resin particle and subsequently the resin particle is released from the compression, the coefficient of variation in the aspect ratio of the resin particle at 25°C after the release from the compression as observed from a direction orthogonal to the direction of the compression is 10% or less.

Description

樹脂粒子、導電性粒子、導電材料及び接続構造体Resin particles, conductive particles, conductive materials and connecting structures
　本発明は、良好な圧縮特性を有する樹脂粒子に関する。また、本発明は、上記樹脂粒子を用いた導電性粒子、導電材料及び接続構造体に関する。 The present invention relates to resin particles having good compression characteristics. The present invention also relates to conductive particles, conductive materials and connecting structures using the above resin particles.
　異方性導電ペースト及び異方性導電フィルム等の異方性導電材料が広く知られている。上記異方性導電材料では、バインダー中に導電性粒子が分散されている。 Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, conductive particles are dispersed in the binder.
　上記異方性導電材料は、フレキシブルプリント基板（ＦＰＣ）、ガラス基板、ガラスエポキシ基板及び半導体チップ等の様々な接続対象部材の電極間を電気的に接続し、接続構造体を得るために用いられている。また、上記導電性粒子として、樹脂粒子と、該樹脂粒子の表面上に配置された導電部とを有する導電性粒子が用いられることがある。 The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit board (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing. Further, as the conductive particles, conductive particles having resin particles and conductive portions arranged on the surface of the resin particles may be used.
　また、液晶表示素子は、２枚のガラス基板間に液晶が配置されて構成されている。該液晶表示素子では、２枚のガラス基板の間隔（ギャップ）を均一かつ一定に保つために、ギャップ制御材としてスペーサが用いられている。該スペーサとして、樹脂粒子が一般に用いられている。 Further, the liquid crystal display element is configured by arranging a liquid crystal between two glass substrates. In the liquid crystal display element, a spacer is used as a gap control material in order to keep the distance (gap) between the two glass substrates uniform and constant. Resin particles are generally used as the spacer.
　下記の特許文献１には、酸性基と、エチレン性不飽和結合を有する基とを側鎖に含有する樹脂（Ａ）と、エチレン性不飽和結合を有する重合性置換基の２つ以上と、前記重合性置換基と結合する２価以上の環構造含有基とを含有する重合性化合物（Ｂ）と、光重合開始剤（Ｃ）とを少なくとも含むカラーフィルタ用の感光性組成物が開示されている。特許文献１には、この感光性組成物が微粒子（Ｄ）を含むことが好ましいこと、及び、感光性組成物を用いてフォトスペーサーを形成できることが記載されている。特許文献１の実施例では、上記感光性組成物により形成されたフォトスペーサーの変形回復率が評価されているものの、該変形回復率は高いことが好ましいことが記載されているにすぎない。 In Patent Document 1 below, a resin (A) containing an acidic group and a group having an ethylenically unsaturated bond in a side chain, and two or more polymerizable substituents having an ethylenically unsaturated bond are described. A photosensitive composition for a color filter containing at least a polymerizable compound (B) containing a divalent or higher valent ring structure-containing group bonded to the polymerizable substituent and a photopolymerization initiator (C) is disclosed. ing. Patent Document 1 describes that it is preferable that this photosensitive composition contains fine particles (D), and that a photospacer can be formed by using the photosensitive composition. In the examples of Patent Document 1, although the deformation recovery rate of the photo spacer formed by the photosensitive composition is evaluated, it is only described that the deformation recovery rate is preferably high.
特開２００９－１６２８７１号公報Japanese Unexamined Patent Publication No. 2009-162871
　従来の導電性粒子では、電極間を導電接続する際に、導電性粒子が十分に変形しなかったり、圧縮された導電性粒子が元の形状に戻ろうとする作用が働いたりすることがある。この場合、導電性粒子と電極（被着体）との接触面積が十分に大きくならなかったり、導電性粒子と電極との界面において剥離が生じたりするなどして、接続抵抗が高くなり、導通信頼性が低下する。 With conventional conductive particles, when conducting conductive connections between electrodes, the conductive particles may not be sufficiently deformed, or the compressed conductive particles may act to return to their original shape. In this case, the contact area between the conductive particles and the electrode (adhesion) is not sufficiently large, or peeling occurs at the interface between the conductive particles and the electrode, resulting in high connection resistance and conduction. Reliability is reduced.
　また、従来の樹脂粒子をスペーサとして用いる場合に、樹脂粒子と接続対象部材（被着体）との接触面積及び摩擦抵抗が十分に大きくならず、樹脂粒子が転がるなどして所定の位置に固定されないことがある。この場合、樹脂粒子と接続対象部材との界面において剥離が生じて、接続対象部材間の厚みを均一に制御することができず、スペーサとしての機能を十分に発揮できないことがある。 Further, when the conventional resin particles are used as a spacer, the contact area and frictional resistance between the resin particles and the member to be connected (adhesive body) are not sufficiently large, and the resin particles are fixed in a predetermined position by rolling or the like. It may not be done. In this case, peeling may occur at the interface between the resin particles and the member to be connected, and the thickness between the members to be connected may not be uniformly controlled, and the function as a spacer may not be sufficiently exhibited.
　本発明の目的は、樹脂粒子又は樹脂粒子を用いた粒子と、被着体との接触面積及び摩擦抵抗を大きくすることができ、従って、樹脂粒子又は樹脂粒子を用いた粒子と、被着体との界面剥離を抑えることができる樹脂粒子を提供することである。また、本発明の目的は、上記樹脂粒子を用いた導電性粒子、導電材料及び接続構造体を提供することである。 An object of the present invention is to increase the contact area and frictional resistance between the resin particles or the particles using the resin particles and the adherend, and therefore, the resin particles or the particles using the resin particles and the adherend. It is to provide resin particles which can suppress the interface peeling with. Another object of the present invention is to provide conductive particles, a conductive material, and a connecting structure using the above resin particles.
　本発明の広い局面によれば、樹脂粒子であって、前記樹脂粒子を粒子径に対して３０％圧縮した状態で２００℃にて１０分間保持した後、圧縮から解放したときに、２５℃にて、圧縮方向と直交する方向から観察される圧縮解放後の前記樹脂粒子のアスペクト比の変動係数が、１０％以下である、樹脂粒子が提供される。 According to a broad aspect of the present invention, the resin particles are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then released to 25 ° C. when released from the compression. Therefore, the resin particles are provided in which the coefficient of variation of the aspect ratio of the resin particles after compression / release observed from a direction orthogonal to the compression direction is 10% or less.
　本発明に係る樹脂粒子のある特定の局面では、前記樹脂粒子は、加熱により熱硬化可能である。 In a specific aspect of the resin particles according to the present invention, the resin particles can be thermoset by heating.
　本発明に係る樹脂粒子のある特定の局面では、熱分解温度が、２００℃以上３５０℃以下である。 In a specific aspect of the resin particles according to the present invention, the thermal decomposition temperature is 200 ° C. or higher and 350 ° C. or lower.
　本発明に係る樹脂粒子のある特定の局面では、１０％圧縮したときの圧縮弾性率が、１００Ｎ／ｍｍ２以上３５００Ｎ／ｍｍ２以下である。 In a specific aspect of the resin particles according to the present invention, the compression elastic modulus of when compressed 10%, it is 100 N / mm 2 or more 3500 N / mm 2 or less.
　本発明に係る樹脂粒子のある特定の局面では、３０％圧縮したときの圧縮弾性率が、１００Ｎ／ｍｍ２以上３０００Ｎ／ｍｍ２以下である。 In a specific aspect of the resin particles according to the present invention, the compressive elastic modulus when compressed by 30% is 100 N / mm 2 or more and 3000 N / mm 2 or less.
　本発明に係る樹脂粒子のある特定の局面では、前記圧縮方向と直交する方向から観察される圧縮解放後の前記樹脂粒子のアスペクト比が、１．１以上である。 In a specific aspect of the resin particles according to the present invention, the aspect ratio of the resin particles after compression / release observed from a direction orthogonal to the compression direction is 1.1 or more.
　本発明に係る樹脂粒子のある特定の局面では、前記樹脂粒子は、スペーサに用いられるか、電子部品用接着剤に用いられるか、導電部を有する導電性粒子を得るために用いられるか、又は、積層造形用材料に用いられる。 In certain aspects of the resin particles according to the present invention, the resin particles are used as spacers, adhesives for electronic parts, or used to obtain conductive particles having a conductive portion. , Used as a material for laminated molding.
　本発明に係る樹脂粒子のある特定の局面では、前記樹脂粒子は、液晶表示素子用スペーサとして用いられるか、電子部品用接着剤として用いられるか、又は、導電部を有する導電性粒子を得るために用いられる。 In a specific aspect of the resin particles according to the present invention, the resin particles are used as a spacer for a liquid crystal display element, an adhesive for an electronic component, or a conductive particle having a conductive portion. Used for.
　本発明の広い局面によれば、上述した樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備える、導電性粒子が提供される。 According to a broad aspect of the present invention, a conductive particle including the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles is provided.
　本発明に係る導電性粒子のある特定の局面では、前記導電性粒子は、前記導電部の外表面上に配置された絶縁性物質をさらに備える。 In certain aspects of the conductive particles according to the present invention, the conductive particles further include an insulating substance disposed on the outer surface of the conductive portion.
　本発明に係る導電性粒子のある特定の局面では、前記導電性粒子は、前記導電部の外表面に突起を有する。 In a specific aspect of the conductive particles according to the present invention, the conductive particles have protrusions on the outer surface of the conductive portion.
　本発明の広い局面によれば、導電性粒子と、バインダー樹脂とを含み、前記導電性粒子が、上述した樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備える、導電材料が提供される。 According to a broad aspect of the present invention, a conductive material containing conductive particles and a binder resin, wherein the conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles. Is provided.
　本発明の広い局面によれば、第１の接続対象部材と、第２の接続対象部材と、前記第１の接続対象部材と前記第２の接続対象部材とを接続している接続部とを備え、前記接続部が、上述した樹脂粒子により形成されているか、又は前記樹脂粒子を含む組成物により形成されている、接続構造体が提供される。 According to a broad aspect of the present invention, a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member are provided. Provided are a connecting structure in which the connecting portion is formed of the resin particles described above or is formed of a composition containing the resin particles.
　本発明の広い局面によれば、第１の電極を表面に有する第１の接続対象部材と、第２の電極を表面に有する第２の接続対象部材と、前記第１の接続対象部材と前記第２の接続対象部材とを接続している接続部とを備え、前記接続部が、導電性粒子により形成されているか、又は前記導電性粒子とバインダー樹脂とを含む導電材料により形成されており、前記導電性粒子が、上述した樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備え、前記第１の電極と前記第２の電極とが前記導電性粒子により電気的に接続されている、接続構造体が提供される。 According to a broad aspect of the present invention, a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, and the above. It is provided with a connecting portion connecting the second connection target member, and the connecting portion is formed of conductive particles or a conductive material containing the conductive particles and a binder resin. The conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles, and the first electrode and the second electrode are electrically formed by the conductive particles. A connected, connected structure is provided.
　本発明に係る樹脂粒子は、該樹脂粒子を粒子径に対して３０％圧縮した状態で２００℃にて１０分間保持した後、圧縮から解放したときに、２５℃にて、圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数が、１０％以下である。本発明に係る樹脂粒子では、上記の構成が備えられているので、樹脂粒子又は樹脂粒子を用いた粒子と、被着体との接触面積及び摩擦抵抗を大きくすることができ、従って、樹脂粒子又は樹脂粒子を用いた粒子と、被着体との界面剥離を抑えることができる。 The resin particles according to the present invention are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then when released from compression, they are orthogonal to the compression direction at 25 ° C. The coefficient of variation of the aspect ratio of the resin particles after compression / release observed from the direction is 10% or less. Since the resin particles according to the present invention have the above-mentioned structure, the contact area and frictional resistance between the resin particles or the particles using the resin particles and the adherend can be increased, and therefore, the resin particles. Alternatively, it is possible to suppress interfacial peeling between the particles using the resin particles and the adherend.
図１は、本発明の第１の実施形態に係る樹脂粒子を示す断面図であり、図１（ａ）は、圧縮前の樹脂粒子を示す断面図であり、図１（ｂ）は、圧縮解放後の樹脂粒子を示す断面図である。FIG. 1 is a cross-sectional view showing resin particles according to the first embodiment of the present invention, FIG. 1A is a cross-sectional view showing resin particles before compression, and FIG. 1B is compression. It is sectional drawing which shows the resin particle after release. 図２は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。FIG. 2 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. 図３は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。FIG. 3 is a cross-sectional view showing the conductive particles according to the second embodiment of the present invention. 図４は、本発明の第３の実施形態に係る導電性粒子を示す断面図である。FIG. 4 is a cross-sectional view showing the conductive particles according to the third embodiment of the present invention. 図５は、本発明の第１の実施形態に係る導電性粒子を用いた接続構造体の一例を示す断面図である。FIG. 5 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention. 図６は、本発明に係る樹脂粒子を用いた電子部品装置の一例を示す断面図である。FIG. 6 is a cross-sectional view showing an example of an electronic component device using the resin particles according to the present invention. 図７は、図６に示す電子部品装置における接合部部分を拡大して示す断面図である。FIG. 7 is an enlarged cross-sectional view showing a joint portion in the electronic component device shown in FIG. 図８（ａ）は、樹脂粒子（熱硬化前の樹脂粒子）の代表的な電子顕微鏡写真であり、図８（ｂ）は、圧縮解放後の樹脂粒子の代表的な電子顕微鏡写真である。FIG. 8A is a typical electron micrograph of the resin particles (resin particles before heat curing), and FIG. 8B is a typical electron micrograph of the resin particles after compression and release. 図９は、実施例８における圧縮解放後の樹脂粒子の電子顕微鏡写真である。FIG. 9 is an electron micrograph of the resin particles after compression release in Example 8. 図１０（ａ）は、比較例１における圧縮解放後の樹脂粒子の電子顕微鏡写真であり、図１０（ｂ）は、比較例２における圧縮解放後の樹脂粒子の電子顕微鏡写真であり、図１０（ｃ）は、比較例３における圧縮解放後の樹脂粒子の電子顕微鏡写真である。FIG. 10 (a) is an electron micrograph of the resin particles after compression and release in Comparative Example 1, and FIG. 10 (b) is an electron micrograph of the resin particles after compression and release in Comparative Example 2. FIG. (C) is an electron micrograph of the resin particles after compression and release in Comparative Example 3.
　以下、本発明の詳細を説明する。 The details of the present invention will be described below.
　（樹脂粒子）
　本発明に係る樹脂粒子は、樹脂粒子を粒子径に対して３０％圧縮した状態で２００℃にて１０分間保持した後、圧縮から解放したときに、２５℃にて、圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数が、１０％以下である。 (Resin particles)
The resin particles according to the present invention are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then released from compression at 25 ° C. in a direction orthogonal to the compression direction. The coefficient of variation of the aspect ratio of the resin particles after compression / release observed from is 10% or less.
　本発明に係る樹脂粒子では、上記の構成が備えられているので、樹脂粒子又は樹脂粒子を用いた粒子と、被着体との接触面積及び摩擦抵抗を大きくすることができ、従って、樹脂粒子又は樹脂粒子を用いた粒子と、被着体との界面剥離を抑えることができる。 Since the resin particles according to the present invention have the above-mentioned structure, the contact area and frictional resistance between the resin particles or the particles using the resin particles and the adherend can be increased, and therefore, the resin particles. Alternatively, it is possible to suppress interfacial peeling between the particles using the resin particles and the adherend.
　本発明に係る樹脂粒子は、加熱により熱硬化させることができる。本発明に係る樹脂粒子は、加熱により熱硬化可能である。本発明に係る樹脂粒子（熱硬化前の樹脂粒子）は、完全に熱硬化しておらず、加熱圧縮したときに、圧縮された形状を良好に維持することができ、かつ複数の樹脂粒子において圧縮された形状を良好に揃えることができる。本発明に係る樹脂粒子において、熱硬化可能であるか否かは以下のように確認することができる。 The resin particles according to the present invention can be thermoset by heating. The resin particles according to the present invention can be thermoset by heating. The resin particles (resin particles before thermosetting) according to the present invention are not completely thermoset, can maintain a good compressed shape when heat-compressed, and have a plurality of resin particles. The compressed shape can be well aligned. Whether or not the resin particles according to the present invention can be thermoset can be confirmed as follows.
　熱硬化前の樹脂粒子を２００℃で１時間加熱した後、２５℃で１時間冷却する。加熱及び冷却後の樹脂粒子を１０％圧縮したときの圧縮弾性率（１０％Ｋ値）と、熱硬化前の樹脂粒子を１０％圧縮したときの圧縮弾性率（１０％Ｋ値）とから、熱硬化前後の圧縮弾性率の変化率を下記式により算出する。下記式により算出される熱硬化前後の弾性率の変化率が１０５％以上である場合に、加熱による熱硬化が生じたとみなし、加熱により熱硬化可能な粒子であるとみなす。なお、樹脂粒子の１０％Ｋ値は後述の方法により測定することができる。 The resin particles before thermosetting are heated at 200 ° C. for 1 hour and then cooled at 25 ° C. for 1 hour. From the compressive elastic modulus (10% K value) when the resin particles after heating and cooling are compressed by 10% and the compressive elastic modulus (10% K value) when the resin particles before thermosetting are compressed by 10%, The rate of change in compressive elastic modulus before and after thermosetting is calculated by the following formula. When the rate of change in elastic modulus before and after thermosetting calculated by the following formula is 105% or more, it is considered that thermosetting by heating has occurred, and the particles are thermosetting by heating. The 10% K value of the resin particles can be measured by the method described later.
　熱硬化前後の圧縮弾性率の変化率（％）＝（加熱及び冷却後の樹脂粒子の１０％Ｋ値）／（熱硬化前の樹脂粒子の１０％Ｋ値）×１００ Rate of change in compressive elastic modulus before and after thermosetting (%) = (10% K value of resin particles after heating and cooling) / (10% K value of resin particles before thermosetting) x 100
　本発明に係る樹脂粒子を、該樹脂粒子の表面上に導電部が形成された導電性粒子として用いる場合には、導電性粒子と電極（被着体）との熱圧着時に導電性粒子が良好に変形し、かつ熱圧着後も圧縮された形状が維持されるので、導電性粒子と電極との接触面積を大きくすることができる。このため、導電性粒子と電極との界面剥離を抑えることができ、さらに、電極の傷付きを効果的に抑えることができる。また、電極間を電気的に接続した場合に、導電性粒子における樹脂粒子と導電部との密着性を高めることができる。したがって、本発明に係る樹脂粒子を用いた導電性粒子では、該導電性粒子により電極間が電気的に接続された接続構造体の接続抵抗を効果的に低くすることができ、導通信頼性を高めることができる。また、上記接続構造体を高温及び高湿条件下で長時間放置しても、接続抵抗が高くなりにくく、導通不良が生じにくい。さらに、上記接続構造体が落下するなどして衝撃が加わったとしても、導電性粒子と電極との界面剥離を抑えることができる。 When the resin particles according to the present invention are used as conductive particles in which a conductive portion is formed on the surface of the resin particles, the conductive particles are good at the time of thermal pressure bonding between the conductive particles and the electrode (adhesion). Since it is deformed into a shape and the compressed shape is maintained even after thermal pressure bonding, the contact area between the conductive particles and the electrode can be increased. Therefore, it is possible to suppress the interfacial peeling between the conductive particles and the electrode, and further, it is possible to effectively suppress the damage to the electrode. Further, when the electrodes are electrically connected, the adhesion between the resin particles and the conductive portion in the conductive particles can be improved. Therefore, in the conductive particles using the resin particles according to the present invention, the connection resistance of the connection structure in which the electrodes are electrically connected by the conductive particles can be effectively lowered, and the continuity reliability can be improved. Can be enhanced. Further, even if the connection structure is left for a long time under high temperature and high humidity conditions, the connection resistance is unlikely to increase and conduction failure is unlikely to occur. Further, even if an impact is applied such as when the connection structure is dropped, the interface peeling between the conductive particles and the electrode can be suppressed.
　また、本発明に係る樹脂粒子をスペーサ（ギャップ材）又は電子部品用接着剤として用いる場合には、樹脂粒子と接続対象部材（被着体）との熱圧着時に樹脂粒子が良好に変形し、かつ熱圧着後も圧縮された形状が維持されるので、樹脂粒子と接続対象部材との接触面積及び摩擦抵抗を大きくすることができ、樹脂粒子を所定の位置に固定しやすい。したがって、本発明に係る樹脂粒子を用いたスペーサ又は電子部品用接着剤では、樹脂粒子と接続対象部材との界面剥離を抑えることができる。本発明に係る樹脂粒子を用いたスペーサ又は電子部品用接着剤では、接続対象部材間の厚みを均一に制御することができる。 Further, when the resin particles according to the present invention are used as a spacer (gap material) or an adhesive for electronic parts, the resin particles are satisfactorily deformed during thermocompression bonding between the resin particles and the member to be connected (adhesive body). Moreover, since the compressed shape is maintained even after thermocompression bonding, the contact area and frictional resistance between the resin particles and the member to be connected can be increased, and the resin particles can be easily fixed at a predetermined position. Therefore, the spacer or the adhesive for electronic parts using the resin particles according to the present invention can suppress the interfacial peeling between the resin particles and the member to be connected. In the spacer or the adhesive for electronic parts using the resin particles according to the present invention, the thickness between the members to be connected can be uniformly controlled.
　本発明に係る樹脂粒子は、樹脂粒子を粒子径に対して３０％圧縮した状態で２００℃にて１０分間保持した後、圧縮から解放したときに、２５℃にて、圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数（ＣＶ値）が、１０％以下である。本発明に係る樹脂粒子は、従来の樹脂粒子とは異なる圧縮特性を有する。 The resin particles according to the present invention are held at 200 ° C. for 10 minutes in a state where the resin particles are compressed by 30% with respect to the particle size, and then released from compression at 25 ° C. in a direction orthogonal to the compression direction. The coefficient of variation (CV value) of the aspect ratio of the resin particles after compression / release observed from is 10% or less. The resin particles according to the present invention have different compression characteristics from the conventional resin particles.
　圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数（ＣＶ値）を１０％以下に制御する方法としては、例えば、柔軟性を有しかつ復元性の低い樹脂粒子を用いる方法が挙げられる。柔軟性を有しかつ復元性の低い樹脂粒子を得る方法としては、例えば、樹脂粒子の作製時の反応温度を低くする方法が挙げられる。より具体的には、樹脂粒子の材料として熱硬化性樹脂を用い、反応温度を８０℃以下（好ましくは７０℃以下）に抑えて作製する方法が挙げられる。 As a method of controlling the coefficient of variation (CV value) of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction to 10% or less, for example, it has flexibility and low recoverability. A method using resin particles can be mentioned. Examples of the method for obtaining the resin particles having flexibility and low resilience include a method of lowering the reaction temperature at the time of producing the resin particles. More specifically, a method of using a thermosetting resin as a material for the resin particles and suppressing the reaction temperature to 80 ° C. or lower (preferably 70 ° C. or lower) can be mentioned.
　上記樹脂粒子の圧縮及び圧縮解放後の樹脂粒子の観察は、具体的には、以下のようにして行われる。 Specifically, the observation of the resin particles after compression and compression release of the resin particles is performed as follows.
　第１の板及び第２の板を用意する。第１の板及び第２の板はそれぞれ、平面を有する。第１の板又は第２の板の表面の末端に、ギャップ材として、樹脂粒子の粒子径の７０％の厚みを有するポリイミドフィルムを貼り付ける。表面温度が２００℃となるように第１の板及び第２の板を加熱する。加熱された第１の板の表面に、樹脂粒子を配置する。万力熱プレス機デジタル（例えば、アズワン社製「ＭＮＰ２－００２Ｄ」）を用いて、第１の板と第２の板との間の距離が、樹脂粒子の粒子径の７０％となる位置まで、第１の板又は第２の板を移動させる。すなわち、樹脂粒子を粒子径に対して３０％圧縮する。第１の板及び第２の板の平面部分にて、樹脂粒子を圧縮する。圧縮条件は、圧縮速度２０００ｍＮ／秒及び荷重２００００ｍＮの条件とする。樹脂粒子を３０％圧縮した状態で、荷重２００００ｍＮで２００℃にて１０分間保持した後、圧縮を解放する。圧縮解放後の樹脂粒子を無風条件下で２５℃にて１時間放置した後、該樹脂粒子を電子顕微鏡又は光学顕微鏡で撮影し、樹脂粒子の形状を観察する。 Prepare the first plate and the second plate. The first plate and the second plate each have a flat surface. A polyimide film having a thickness of 70% of the particle diameter of the resin particles is attached as a gap material to the end of the surface of the first plate or the second plate. The first plate and the second plate are heated so that the surface temperature becomes 200 ° C. Resin particles are placed on the surface of the heated first plate. Using a vise heat press digital (for example, "MNP2-002D" manufactured by AS ONE Corporation), until the distance between the first plate and the second plate is 70% of the particle size of the resin particles. , Move the first plate or the second plate. That is, the resin particles are compressed by 30% with respect to the particle size. The resin particles are compressed in the flat portions of the first plate and the second plate. The compression conditions are a compression speed of 2000 mN / sec and a load of 20000 mN. With the resin particles compressed by 30%, the resin particles are held at 200 ° C. for 10 minutes under a load of 20000 mN, and then the compression is released. After the resin particles after compression and release are left at 25 ° C. for 1 hour under windless conditions, the resin particles are photographed with an electron microscope or an optical microscope, and the shape of the resin particles is observed.
　上記第１の板及び上記第２の板の材質は、ガラス、ステンレス（ＳＵＳ）、又はシリコンであることが好ましく、ガラスであることがより好ましい。 The material of the first plate and the second plate is preferably glass, stainless steel (SUS), or silicon, and more preferably glass.
　上記樹脂粒子の粒子径は、平均粒子径であることが好ましく、数平均粒子径であることが好ましい。なお、樹脂粒子の粒子径の測定方法は後述する。 The particle size of the resin particles is preferably an average particle size, and preferably a number average particle size. The method for measuring the particle size of the resin particles will be described later.
　本発明の効果をより一層効果的に発揮させる観点からは、圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数（ＣＶ値）は、１０％以下であり、好ましくは７％以下、より好ましくは５％以下である。圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数は小さいほうが好ましい。圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数は、１％以上であってもよく、３％以上であってもよい。上記圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の変動係数（ＣＶ値）は、任意の樹脂粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、各樹脂粒子のアスペクト比の平均値及び標準偏差を算出することにより求めることが好ましい。 From the viewpoint of exerting the effect of the present invention more effectively, the coefficient of variation (CV value) of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction is 10% or less. It is preferably 7% or less, more preferably 5% or less. It is preferable that the coefficient of variation of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction is small. The coefficient of variation of the aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction may be 1% or more, or 3% or more. The coefficient of variation (CV value) of the aspect ratio of the resin particles after compression and release observed from the direction orthogonal to the compression direction is obtained by observing 50 arbitrary resin particles with an electron microscope or an optical microscope and each resin particle. It is preferable to obtain the average value and standard deviation of the aspect ratios of.
　上記ＣＶ値は、下記式で表される。 The above CV value is expressed by the following formula.
　ＣＶ値（％）＝（ρ／Ｘｎ）×１００
　ρ：圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の標準偏差
　Ｘｎ：圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比の平均値 CV value (%) = (ρ / Xn) × 100
ρ: Standard deviation of the aspect ratio of the resin particles after compression / release observed from a direction orthogonal to the compression direction Xn: Mean value of the aspect ratios of the resin particles after compression / release observed from a direction orthogonal to the compression direction
　なお、上記樹脂粒子は、例えば、２００℃で加熱して用いられなくてもよく、３０％圧縮した状態で用いられなくてもよい。上記樹脂粒子の圧縮及び圧縮解放後の樹脂粒子の観察は、樹脂粒子の圧縮特性を評価するために行われる。 The resin particles may not be used by heating at 200 ° C., for example, and may not be used in a state of being compressed by 30%. Observation of the resin particles after compression and compression release of the resin particles is performed in order to evaluate the compression characteristics of the resin particles.
　圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比は、一般的に１を超える。圧縮方向と直交する方向から観察される圧縮解放後の上記樹脂粒子のアスペクト比は、１．１以上であることが好ましく、１．３以上であることがより好ましく、５以下であることが好ましく、３以下であることがより好ましく、２以下であることがさらに好ましく、１．５以下であることが特に好ましい。上記アスペクト比が上記下限以上及び上記上限以下であると、樹脂粒子又は樹脂粒子を用いた粒子と接続対象部材との接触面積及び摩擦抵抗を大きくすることができ、樹脂粒子又は樹脂粒子を用いた粒子を所定の位置に固定しやすくなる。 The aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction generally exceeds 1. The aspect ratio of the resin particles after compression / release observed from the direction orthogonal to the compression direction is preferably 1.1 or more, more preferably 1.3 or more, and preferably 5 or less. It is more preferably 3 or less, further preferably 2 or less, and particularly preferably 1.5 or less. When the aspect ratio is at least the above lower limit and at least the above upper limit, the contact area and frictional resistance between the resin particles or the particles using the resin particles and the member to be connected can be increased, and the resin particles or the resin particles are used. It becomes easier to fix the particles in place.
　図１は、本発明の第１の実施形態に係る樹脂粒子を示す断面図である。図１（ａ）は、圧縮前の樹脂粒子を示す断面図であり、図１（ｂ）は、圧縮解放後の樹脂粒子を示す断面図である。なお、図８（ａ）に、樹脂粒子（熱硬化前の樹脂粒子）の代表的な電子顕微鏡写真を示し、図８（ｂ）に、圧縮解放後の樹脂粒子の代表的な電子顕微鏡写真を示す。 FIG. 1 is a cross-sectional view showing resin particles according to the first embodiment of the present invention. FIG. 1A is a cross-sectional view showing the resin particles before compression, and FIG. 1B is a cross-sectional view showing the resin particles after compression release. 8 (a) shows a typical electron micrograph of the resin particles (resin particles before heat curing), and FIG. 8 (b) shows a typical electron micrograph of the resin particles after compression and release. Shown.
　図１（ａ）に示す圧縮前の樹脂粒子１の形状は球形である。図１（ｂ）に示す圧縮解放後の樹脂粒子１は、図１（ａ）に示す樹脂粒子１を粒子径に対して３０％圧縮した状態で２００℃にて１０分間保持した後、圧縮から解放したときの、圧縮解放後の樹脂粒子である。図１（ｂ）に示す圧縮解放後の樹脂粒子１は、圧縮方向Ｐにおいて、互いに対向する第１の表面１ａ（平面部分）と第２の表面１ｂ（平面部分）とを有する。第１の表面１ａ及び第２の表面１ｂは、樹脂粒子１の３０％圧縮時に用いられた第１の板及び第２の板の表面に由来して形成される。第１の表面１ａ及び第２の表面１ｂは、平面である。第１の表面１ａ及び第２の表面１ｂの形状はそれぞれ、円形である。 The shape of the resin particles 1 before compression shown in FIG. 1A is spherical. The resin particles 1 after compression and release shown in FIG. 1 (b) are obtained by holding the resin particles 1 shown in FIG. 1 (a) at 200 ° C. for 10 minutes in a state of being compressed by 30% with respect to the particle size, and then from compression. These are the resin particles after compression release when released. The compressed and released resin particles 1 shown in FIG. 1B have a first surface 1a (flat surface portion) and a second surface 1b (flat surface portion) facing each other in the compression direction P. The first surface 1a and the second surface 1b are formed from the surfaces of the first plate and the second plate used during the 30% compression of the resin particles 1. The first surface 1a and the second surface 1b are flat surfaces. The shapes of the first surface 1a and the second surface 1b are circular, respectively.
　圧縮方向と直交する方向から観察される圧縮解放後の樹脂粒子の短径をＡとする。圧縮方向と直交する方向から観察される圧縮解放後の樹脂粒子の長径をＢとする。圧縮解放後の上記樹脂粒子のアスペクト比は、Ｂ／Ａで表される。上記短径（Ａ）は、圧縮方向における樹脂粒子の径であることが好ましい。長径（Ｂ）は、圧縮方向と直交する方向における樹脂粒子の径であることが好ましい。図１（ｂ）に示す圧縮解放後の樹脂粒子１では、Ａは、第１の表面１ａと第２の表面１ｂとの距離である。また、図１（ｂ）に示す圧縮解放後の樹脂粒子１では、Ｂは、圧縮方向Ｐと直交する方向における樹脂粒子１の長径である。 Let A be the minor axis of the resin particles after compression release observed from the direction orthogonal to the compression direction. Let B be the major axis of the resin particles after compression release observed from the direction orthogonal to the compression direction. The aspect ratio of the resin particles after compression release is represented by B / A. The minor axis (A) is preferably the diameter of the resin particles in the compression direction. The major axis (B) is preferably the diameter of the resin particles in the direction orthogonal to the compression direction. In the resin particles 1 after compression release shown in FIG. 1B, A is the distance between the first surface 1a and the second surface 1b. Further, in the resin particles 1 after compression / release shown in FIG. 1B, B is the major axis of the resin particles 1 in the direction orthogonal to the compression direction P.
　圧縮解放後の樹脂粒子は、圧縮方向において互いに対向する２つの平面部分を有していなくてもよい。 The resin particles after compression release do not have to have two flat portions facing each other in the compression direction.
　上記樹脂粒子（圧縮前）のアスペクト比は、好ましくは２以下、より好ましくは１．５以下、さらに好ましくは１．２以下である。上記樹脂粒子（圧縮前）のアスペクト比は、長径／短径を示す。上記樹脂粒子（圧縮前）のアスペクト比は、任意の樹脂粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、最大径と最小径をそれぞれ長径、短径とし、各樹脂粒子の長径／短径の平均値を算出することにより求めることが好ましい。 The aspect ratio of the resin particles (before compression) is preferably 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less. The aspect ratio of the resin particles (before compression) indicates a major axis / minor axis. The aspect ratio of the resin particles (before compression) is such that 50 arbitrary resin particles are observed with an electron microscope or an optical microscope, the maximum diameter and the minimum diameter are set to the major axis and the minor axis, respectively, and the major axis / minor axis of each resin particle. It is preferable to obtain by calculating the average value of.
　上記樹脂粒子（圧縮前）の粒子径は、用途に応じて適宜設定することができる。上記樹脂粒子（圧縮前）の粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上であり、好ましくは５００μｍ以下、より好ましくは１００μｍ以下、さらに好ましくは５０μｍ以下、特に好ましくは２０μｍ以下、最も好ましくは１０μｍ以下である。上記樹脂粒子の粒子径が上記下限以上及び上記上限以下であると、樹脂粒子を導電性粒子及びスペーサの用途により一層好適に使用可能になる。 The particle size of the resin particles (before compression) can be appropriately set according to the application. The particle size of the resin particles (before compression) is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 20 μm or less. Most preferably, it is 10 μm or less. When the particle diameter of the resin particles is not less than the above lower limit and not more than the above upper limit, the resin particles can be used more preferably depending on the use of the conductive particles and the spacer.
　上記樹脂粒子（圧縮前）の粒子径は、平均粒子径であることが好ましく、数平均粒子径であることが好ましい。上記樹脂粒子の粒子径は、例えば、任意の樹脂粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、各樹脂粒子の粒子径の平均値を算出することや、粒度分布測定装置を用いて求められる。電子顕微鏡又は光学顕微鏡での観察では、１個当たりの樹脂粒子の粒子径は、円相当径での粒子径として求められる。電子顕微鏡又は光学顕微鏡での観察において、任意の５０個の樹脂粒子の円相当径での平均粒子径は、球相当径での平均粒子径とほぼ等しくなる。粒度分布測定装置では、１個当たりの樹脂粒子の粒子径は、球相当径での粒子径として求められる。上記樹脂粒子の平均粒子径は、粒度分布測定装置を用いて算出することが好ましい。 The particle size of the resin particles (before compression) is preferably an average particle size, and preferably a number average particle size. The particle size of the resin particles can be obtained, for example, by observing 50 arbitrary resin particles with an electron microscope or an optical microscope, calculating the average value of the particle size of each resin particle, or using a particle size distribution measuring device. Be done. In observation with an electron microscope or an optical microscope, the particle size of each resin particle is determined as the particle size in the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 resin particles in the circle equivalent diameter is substantially equal to the average particle diameter in the sphere equivalent diameter. In the particle size distribution measuring device, the particle size of each resin particle is obtained as the particle size in the equivalent diameter of a sphere. The average particle size of the resin particles is preferably calculated using a particle size distribution measuring device.
　また、導電性粒子において、上記樹脂粒子の粒子径を測定する場合には、例えば、以下のようにして測定できる。 Further, when measuring the particle size of the resin particles in the conductive particles, for example, the measurement can be performed as follows.
　導電性粒子の含有量が３０重量％となるように、Ｋｕｌｚｅｒ社製「テクノビット４０００」に添加し、分散させて、導電性粒子検査用埋め込み樹脂体を作製する。検査用埋め込み樹脂体中に分散した導電性粒子の中心付近を通るようにイオンミリング装置（日立ハイテクノロジーズ社製「ＩＭ４０００」）を用いて、導電性粒子の断面を切り出す。そして、電界放射型走査型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて、画像倍率を２５０００倍に設定し、５０個の導電性粒子を無作為に選択し、各導電性粒子の樹脂粒子を観察する。各導電性粒子における樹脂粒子の粒子径を計測し、それらを算術平均して樹脂粒子の粒子径とする。 Add to "Technobit 4000" manufactured by Kulzer so that the content of conductive particles is 30% by weight, and disperse to prepare an embedded resin body for conducting conductive particle inspection. A cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the embedded resin body for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification is set to 25000 times, 50 conductive particles are randomly selected, and the resin particles of each conductive particle are observed. .. The particle size of the resin particles in each conductive particle is measured, and they are arithmetically averaged to obtain the particle size of the resin particles.
　上記樹脂粒子の粒子径の変動係数（ＣＶ値）は、好ましくは１５％以下、より好ましくは１０％以下、さらに好ましくは５％以下である。上記ＣＶ値が上記上限以下であると、樹脂粒子を導電性粒子及びスペーサの用途により一層好適に使用可能になる。 The coefficient of variation (CV value) of the particle size of the resin particles is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less. When the CV value is not more than the above upper limit, the resin particles can be more preferably used depending on the use of the conductive particles and the spacer.
　上記ＣＶ値は、下記式で表される。 The above CV value is expressed by the following formula.
　ＣＶ値（％）＝（ρ／Ｄｎ）×１００
　ρ：樹脂粒子の粒子径の標準偏差
　Ｄｎ：樹脂粒子の粒子径の平均値 CV value (%) = (ρ / Dn) × 100
ρ: Standard deviation of particle size of resin particles Dn: Mean value of particle size of resin particles
　上記樹脂粒子（圧縮前）の形状は特に限定されない。上記樹脂粒子（圧縮前）の形状は、球状であってもよく、球状以外の形状であってもよく、扁平状等の形状であってもよい。 The shape of the resin particles (before compression) is not particularly limited. The shape of the resin particles (before compression) may be spherical, non-spherical, flat or the like.
　上記樹脂粒子の熱分解温度は、好ましくは２００℃以上、より好ましくは２２０℃以上、好ましくは３５０℃以下、より好ましくは３００℃以下である。上記樹脂粒子の熱分解温度が上記下限以上及び上記上限以下であると、圧縮解放後の樹脂粒子の形状を良好にすることができ、本発明の効果をより一層効果的に発揮することができる。 The thermal decomposition temperature of the resin particles is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 350 ° C. or lower, and more preferably 300 ° C. or lower. When the thermal decomposition temperature of the resin particles is not less than the above lower limit and not more than the above upper limit, the shape of the resin particles after compression release can be improved, and the effect of the present invention can be more effectively exhibited. ..
　上記熱分解温度は、示差熱熱重量同時測定装置（例えば、日立ハイテクサイエンス社製「ＴＧ／ＤＴＡ：ＳＴＡ７２００」）を用いて測定可能である。上記樹脂粒子１０ｍｇを空気中で５℃／ｍｉｎで昇温し、測定結果における重量が１０％減少したときの温度を熱分解温度とする。 The thermal decomposition temperature can be measured using a differential thermogravimetric simultaneous measuring device (for example, "TG / DTA: STA7200" manufactured by Hitachi High-Tech Science Co., Ltd.). The temperature at which 10 mg of the resin particles is raised in air at 5 ° C./min and the weight in the measurement result is reduced by 10% is defined as the thermal decomposition temperature.
　上記樹脂粒子を１０％圧縮したときの圧縮弾性率（１０％Ｋ値）は、好ましくは１００Ｎ／ｍｍ２以上、より好ましくは５００Ｎ／ｍｍ２以上、更に好ましくは１０００Ｎ／ｍｍ２以上、好ましくは３５００Ｎ／ｍｍ２以下、より好ましくは３２００Ｎ／ｍｍ２以下、更に好ましくは２８００Ｎ／ｍｍ２以下である。上記１０％Ｋ値が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The compressive modulus (10% K value) when the resin particles are compressed by 10% is preferably 100 N / mm 2 or more, more preferably 500 N / mm 2 or more, still more preferably 1000 N / mm 2 or more, preferably 3500 N. / Mm 2 or less, more preferably 3200 N / mm 2 or less, still more preferably 2800 N / mm 2 or less. When the 10% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記樹脂粒子を３０％圧縮したときの圧縮弾性率（３０％Ｋ値）は、好ましくは１００Ｎ／ｍｍ２以上、より好ましくは３００Ｎ／ｍｍ２以上、更に好ましくは５００Ｎ／ｍｍ２以上、好ましくは３０００Ｎ／ｍｍ２以下、より好ましくは２５００Ｎ／ｍｍ２以下、更に好ましくは２０００Ｎ／ｍｍ２以下である。上記３０％Ｋ値が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The compressive elastic modulus (30% K value) when the resin particles are compressed by 30% is preferably 100 N / mm 2 or more, more preferably 300 N / mm 2 or more, still more preferably 500 N / mm 2 or more, preferably 3000 N. / mm 2 or less, more preferably 2500N / mm 2, more preferably not more than 2000N / mm 2. When the 30% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記樹脂粒子の上記圧縮弾性率（１０％Ｋ値及び３０％Ｋ値）は、以下のようにして測定できる。 The compressive elastic modulus (10% K value and 30% K value) of the resin particles can be measured as follows.
　微小圧縮試験機を用いて、円柱（直径５０μｍ、ダイヤモンド製）の平滑圧子端面で、２５℃、圧縮速度０．３ｍＮ／秒、及び最大試験荷重２０ｍＮの条件下で樹脂粒子１個を圧縮する。このときの荷重値（Ｎ）及び圧縮変位（ｍｍ）を測定する。得られた測定値から、上記圧縮弾性率（１０％Ｋ値及び３０％Ｋ値）を下記式により求めることができる。上記微小圧縮試験機として、例えば、フィッシャー社製「フィッシャースコープＨ－１００」等が用いられる。上記樹脂粒子における上記圧縮弾性率（１０％Ｋ値及び３０％Ｋ値）は、任意に選択された５０個の樹脂粒子の上記圧縮弾性率（１０％Ｋ値及び３０％Ｋ値）を算術平均することにより、算出することが好ましい。 Using a microcompression tester, compress one resin particle with a smoothing indenter end face of a cylinder (diameter 50 μm, made of diamond) under the conditions of 25 ° C., a compression rate of 0.3 mN / sec, and a maximum test load of 20 mN. The load value (N) and compressive displacement (mm) at this time are measured. From the obtained measured values, the compressive elastic modulus (10% K value and 30% K value) can be calculated by the following formula. As the microcompression tester, for example, "Fisherscope H-100" manufactured by Fisher Co., Ltd. is used. The compressive elastic modulus (10% K value and 30% K value) of the resin particles is an arithmetic mean of the compressive elastic moduli (10% K value and 30% K value) of 50 arbitrarily selected resin particles. It is preferable to calculate by doing so.
　１０％Ｋ値及び３０％Ｋ値（Ｎ／ｍｍ２）＝（３／２１／２）・Ｆ・Ｓ－３／２・Ｒ－１／２
　Ｆ：樹脂粒子が１０％又は３０％圧縮変形したときの荷重値（Ｎ）
　Ｓ：樹脂粒子が１０％又は３０％圧縮変形したときの圧縮変位（ｍｍ）
　Ｒ：樹脂粒子の半径（ｍｍ） 10% K value and 30% K value (N / mm 2 ) = (3/2 1/2 ) ・ F ・ S -3/2・ R- 1 / 2
F: Load value (N) when the resin particles are compressed and deformed by 10% or 30%.
S: Compressive displacement (mm) when the resin particles are compressed and deformed by 10% or 30%
R: Radius of resin particles (mm)
　上記圧縮弾性率は、樹脂粒子の硬さを普遍的かつ定量的に表す。上記圧縮弾性率の使用により、樹脂粒子の硬さを定量的かつ一義的に表すことができる。 The compressive elastic modulus universally and quantitatively represents the hardness of the resin particles. By using the compressive elastic modulus, the hardness of the resin particles can be expressed quantitatively and uniquely.
　上記樹脂粒子の圧縮回復率は、好ましくは５％以上、より好ましくは８％以上であり、好ましくは６０％以下、より好ましくは４０％以下である。上記圧縮回復率が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The compression recovery rate of the resin particles is preferably 5% or more, more preferably 8% or more, preferably 60% or less, and more preferably 40% or less. When the compression recovery rate is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記樹脂粒子の圧縮回復率は、以下のようにして測定できる。 The compression recovery rate of the resin particles can be measured as follows.
　試料台上に樹脂粒子を散布する。散布された１個の樹脂粒子について、微小圧縮試験機を用いて、円柱（直径５０μｍ、ダイヤモンド製）の平滑圧子端面で、２５℃で、樹脂粒子の中心方向に、樹脂粒子が３０％圧縮変形するまで負荷（反転荷重値）を与える。その後、原点用荷重値（０．４０ｍＮ）まで除荷を行う。この間の荷重－圧縮変位を測定し、下記式から圧縮回復率を求めることができる。なお、負荷速度は０．３３ｍＮ／秒とする。上記微小圧縮試験機として、例えば、フィッシャー社製「フィッシャースコープＨ－１００」等が用いられる。 Spray resin particles on the sample table. For one sprayed resin particle, 30% compression deformation of the resin particle toward the center of the resin particle at 25 ° C. on the smoothing indenter end face of a cylinder (diameter 50 μm, made of diamond) using a microcompression tester. A load (reversal load value) is applied until After that, the load is removed to the origin load value (0.40 mN). The load-compressive displacement during this period can be measured, and the compression recovery rate can be calculated from the following formula. The load speed is 0.33 mN / sec. As the microcompression tester, for example, "Fisherscope H-100" manufactured by Fisher Co., Ltd. is used.
　圧縮回復率（％）＝［Ｌ２／Ｌ１］×１００
　Ｌ１：負荷を与えるときの原点用荷重値から反転荷重値に至るまでの圧縮変位
　Ｌ２：負荷を解放するときの反転荷重値から原点用荷重値に至るまでの除荷変位 Compression recovery rate (%) = [L2 / L1] x 100
L1: Compressive displacement from the origin load value when a load is applied to the reversing load value L2: Unloading displacement from the reversing load value when the load is released to the origin load value
　上記樹脂粒子の用途は特に限定されない。上記樹脂粒子は、様々な用途に好適に用いられる。使用時の上記樹脂粒子の圧縮条件を変更することにより、樹脂粒子の厚みを好適に変化させることができる。 The use of the above resin particles is not particularly limited. The resin particles are suitably used for various purposes. By changing the compression conditions of the resin particles at the time of use, the thickness of the resin particles can be suitably changed.
　上記樹脂粒子は、スペーサに用いられるか、電子部品用接着剤に用いられるか、導電部を有する導電性粒子を得るために用いられるか、又は、積層造形用材料に用いられることが好ましい。上記樹脂粒子は、スペーサとして用いられるか、電子部品用接着剤として用いられるか、又は、導電部を有する導電性粒子を得るために用いられることがより好ましい。上記導電性粒子において、上記導電部は、上記樹脂粒子の表面上に形成される。 It is preferable that the resin particles are used for spacers, adhesives for electronic parts, for obtaining conductive particles having conductive portions, or for laminated modeling materials. It is more preferable that the resin particles are used as a spacer, an adhesive for electronic parts, or used to obtain conductive particles having a conductive portion. In the conductive particles, the conductive portion is formed on the surface of the resin particles.
　上記樹脂粒子は、スペーサに用いられるか又はスペーサとして用いられることが好ましい。上記スペーサの使用方法としては、液晶表示素子用スペーサ、ギャップ制御用スペーサ、応力緩和用スペーサ、及び調光積層体用スペーサ等が挙げられる。上記ギャップ制御用スペーサは、スタンドオフ高さ及び平坦性を確保するための積層チップのギャップ制御、並びに、ガラス面の平滑性及び接着剤層の厚みを確保するための光学部品のギャップ制御等に用いることができる。上記応力緩和用スペーサは、センサチップ等の応力緩和、及び２つの接続対象部材を接続している接続部の応力緩和等に用いることができる。上記センサチップとしては、例えば、半導体センサチップ等が挙げられる。 The resin particles are preferably used as a spacer or as a spacer. Examples of the method of using the spacer include a spacer for a liquid crystal display element, a spacer for gap control, a spacer for stress relaxation, and a spacer for a dimming laminate. The gap control spacer is used for gap control of laminated chips for ensuring standoff height and flatness, and for gap control of optical components for ensuring smoothness of glass surface and thickness of adhesive layer. Can be used. The stress relaxation spacer can be used for stress relaxation of a sensor chip or the like, stress relaxation of a connecting portion connecting two members to be connected, and the like. Examples of the sensor chip include a semiconductor sensor chip and the like.
　上記樹脂粒子は、液晶表示素子用スペーサに用いられるか又は液晶表示素子用スペーサとして用いられることが好ましく、液晶表示素子用周辺シール剤に用いられることが好ましい。上記樹脂粒子は、液晶表示用スペーサとして用いられるか、電子部品用接着剤として用いられるか、又は、導電部を有する導電性粒子を得るために用いられることが好ましい。上記液晶表示素子用周辺シール剤において、上記樹脂粒子は、スペーサとして機能することが好ましい。上記樹脂粒子は、良好な圧縮変形特性を有するので、上記樹脂粒子をスペーサとして用いて基板間に配置したり、表面に導電部を形成して導電性粒子として用いて電極間を電気的に接続したりした場合に、スペーサ又は導電性粒子が、基板間又は電極間に効率的に配置される。さらに、上記樹脂粒子では、スペーサの凝集及び移動を抑制することができるので、上記液晶表示素子用スペーサを用いた液晶表示素子及び上記導電性粒子を用いた接続構造体において、接続不良及び表示不良が生じ難くなる。 The resin particles are preferably used as a spacer for a liquid crystal display element or as a spacer for a liquid crystal display element, and preferably used as a peripheral sealant for a liquid crystal display element. The resin particles are preferably used as a spacer for displaying a liquid crystal, used as an adhesive for an electronic component, or used for obtaining conductive particles having a conductive portion. In the peripheral sealant for a liquid crystal display element, the resin particles preferably function as spacers. Since the resin particles have good compressive deformation characteristics, the resin particles can be arranged between substrates by using the resin particles as spacers, or a conductive portion is formed on the surface and used as conductive particles to electrically connect the electrodes. Spacers or conductive particles are efficiently placed between the substrates or between the electrodes when they are used. Further, since the resin particles can suppress the aggregation and movement of the spacers, the connection failure and the display failure in the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles Is less likely to occur.
　上記樹脂粒子は、電子部品用接着剤に用いられるか又は電子部品用接着剤として用いられることが好ましい。上記電子部品用接着剤としては、液晶パネル用接着剤、積層基板用接着剤、基板回路用接着剤、及びカメラモジュール用接着剤等が挙げられる。上記積層基板としては、例えば、半導体センサチップ等が挙げられる。上記電子部品用接着剤に用いられる樹脂粒子又は上記電子部品用接着剤として用いられる樹脂粒子は、接着性能を有する接着性樹脂粒子であることが好ましい。上記樹脂粒子が接着性樹脂粒子であると、圧着して樹脂粒子が硬化する際に、樹脂粒子と積層対象部材とを良好に接着することができる。上記樹脂粒子は単体で、電子部品用接着剤として用いることができる。他の接着成分を用いずに、上記樹脂粒子は、電子部品用接着剤として用いることができる。上記樹脂粒子を電子部品用接着剤に用いる場合、単体で電子部品用接着剤として用いなくてもよく、他の接着成分と共に用いられてもよい。また、上記樹脂粒子が接着性能を有する接着性樹脂粒子である場合は、スペーサ兼電子部品用接着剤として用いることもできる。上記樹脂粒子をスペーサ兼電子部品用接着剤として用いる場合、スペーサと接着剤とが別の材料によって構成される場合と比較して、ギャップ制御性や応力緩和性等のスペーサに求められる物性と、接着性との両立をより一層高度に実現することができる。 The resin particles are preferably used as an adhesive for electronic parts or as an adhesive for electronic parts. Examples of the adhesive for electronic components include an adhesive for liquid crystal panels, an adhesive for laminated substrates, an adhesive for substrate circuits, and an adhesive for camera modules. Examples of the laminated substrate include a semiconductor sensor chip and the like. The resin particles used in the adhesive for electronic parts or the resin particles used as the adhesive for electronic parts are preferably adhesive resin particles having adhesive performance. When the resin particles are adhesive resin particles, the resin particles and the member to be laminated can be satisfactorily adhered to each other when the resin particles are cured by pressure bonding. The resin particles can be used alone as an adhesive for electronic parts. The resin particles can be used as an adhesive for electronic components without using other adhesive components. When the resin particles are used as an adhesive for electronic parts, they may not be used alone as an adhesive for electronic parts, or may be used together with other adhesive components. Further, when the resin particles are adhesive resin particles having adhesive performance, they can also be used as a spacer and an adhesive for electronic parts. When the above resin particles are used as a spacer and an adhesive for electronic parts, the physical properties required for the spacer such as gap controllability and stress relaxation property are as compared with the case where the spacer and the adhesive are made of different materials. It is possible to achieve a higher degree of compatibility with adhesiveness.
　上記樹脂粒子は、積層造形用材料に用いられることが好ましい。上記樹脂粒子を上記積層造形用材料に用いる場合、例えば、上記樹脂粒子を立体的に積層して特定の形状を形成した後に、硬化させることによって立体的な造形物を形成することができる。 The resin particles are preferably used as a material for laminated modeling. When the resin particles are used as the material for laminated modeling, for example, a three-dimensional model can be formed by three-dimensionally laminating the resin particles to form a specific shape and then curing the resin particles.
　以下、樹脂粒子の他の詳細を説明する。なお、本明細書において、「（メタ）アクリレート」は「アクリレート」と「メタクリレート」との一方又は双方を意味し、「（メタ）アクリル」は「アクリル」と「メタクリル」との一方又は双方を意味する。 The other details of the resin particles will be described below. In the present specification, "(meth) acrylate" means one or both of "acrylate" and "methacrylate", and "(meth) acrylic" means one or both of "acrylic" and "methacrylic". means.
　（樹脂粒子の他の詳細）
　上記樹脂粒子の材料は特に限定されない。上記樹脂粒子の材料は、有機材料であることが好ましい。上記樹脂粒子は、多孔構造を有する粒子であってもよく、中実構造を有する粒子であってもよい。上記多孔構造は、複数の細孔を有する構造を意味している。上記中実構造は、複数の細孔を有しない構造を意味している。 (Other details of resin particles)
The material of the resin particles is not particularly limited. The material of the resin particles is preferably an organic material. The resin particles may be particles having a porous structure or particles having a solid structure. The porous structure means a structure having a plurality of pores. The solid structure means a structure having no plurality of pores.
　以下に示すように様々な樹脂粒子の材料が存在する中で、本発明では、上記の特定の圧縮特性を満足させることができる材料が用いられる。 Among various resin particle materials as shown below, in the present invention, a material capable of satisfying the above-mentioned specific compression characteristics is used.
　上記有機材料としては、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリイソブチレン、ポリブタジエン等のポリオレフィン樹脂；ポリメチルメタクリレート及びポリメチルアクリレート等のアクリル樹脂；ポリカーボネート、ポリアミド、フェノールホルムアルデヒド樹脂、メラミンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂、フェノール樹脂、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、エポキシ樹脂、ウレタン樹脂、イソシアネート樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ポリエチレンテレフタレート、ポリスルホン、ポリフェニレンオキサイド、ポリアセタール、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリエーテルスルホン、ジビニルベンゼン重合体、並びにジビニルベンゼン共重合体等が挙げられる。上記ジビニルベンゼン共重合体等としては、ジビニルベンゼン－スチレン共重合体及びジビニルベンゼン－（メタ）アクリル酸エステル共重合体等が挙げられる。 Examples of the organic material include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene; acrylic resins such as polymethylmethacrylate and polymethylacrylate; polycarbonate, polyamide, phenolformaldehyde resin and melamine. Formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, urethane resin, isocyanate resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal , Polystyrene, Polypropyleneimide, Polyether Ether Ketone, Polyethersulfone, Divinylbenzene Polymer, Divinylbenzene Copolymer and the like. Examples of the divinylbenzene copolymer and the like include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylic acid ester copolymer.
　上記樹脂粒子の材料は、エポキシ樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ウレタン樹脂、イソシアネート樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、フェノール樹脂、又はエチレン性不飽和基を有する重合性単量体を１種又は２種以上重合させた重合体であることが好ましい。上記樹脂粒子の材料は、エポキシ樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、フェノール樹脂、又はエチレン性不飽和基を有する重合性単量体を１種又は２種以上重合させた重合体であることがより好ましい。上記樹脂粒子の材料は、熱硬化性樹脂を含むことが更に好ましい。上記熱硬化性樹脂としては、例えば、エポキシ樹脂、メラミン樹脂、ウレタン樹脂、ポリイミド樹脂、及びフェノール樹脂等が挙げられるが、他の熱硬化性樹脂を用いてもよい。上記樹脂粒子の材料は、エポキシ樹脂であることが特に好ましい。上記樹脂粒子の材料が、上記の好ましい態様を満足すると、樹脂粒子の圧縮特性を好適な範囲により一層容易に制御することができる。 The material of the resin particles is an epoxy resin, a melamine resin, a benzoguanamine resin, a urethane resin, an isocyanate resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a phenol resin, or a polymerizable monomer having an ethylenically unsaturated group. It is preferably a seed or a polymer obtained by polymerizing two or more kinds. The material of the resin particles is one or more polymerized epoxy resin, melamine resin, benzoguanamine resin, polyimide resin, polyamide resin, polyamideimide resin, phenol resin, or polymerizable monomer having an ethylenically unsaturated group. It is more preferable that it is a polymer. It is more preferable that the material of the resin particles contains a thermosetting resin. Examples of the thermosetting resin include epoxy resin, melamine resin, urethane resin, polyimide resin, phenol resin and the like, but other thermosetting resins may be used. The material of the resin particles is particularly preferably an epoxy resin. When the material of the resin particles satisfies the above-mentioned preferable aspects, the compression characteristics of the resin particles can be more easily controlled in a suitable range.
　上記樹脂粒子の材料としてエポキシ樹脂を用いる場合には、上記エポキシ樹脂は多官能エポキシ樹脂であることが好ましい。上記エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、及びビスフェノールＦ型エポキシ樹脂等の２官能エポキシ樹脂、トリアジン型エポキシ樹脂、及びグリシジルアミン型エポキシ樹脂等の３官能エポキシ樹脂、並びに、テトラキスフェノールエタン型エポキシ樹脂、及びグリシジルアミン型エポキシ樹脂等の４官能エポキシ樹脂等が挙げられる。上記エポキシ樹脂は１種のみが用いられてもよく、２種以上が併用されてもよい。 When an epoxy resin is used as the material for the resin particles, the epoxy resin is preferably a polyfunctional epoxy resin. Examples of the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, trifunctional epoxy resins such as triazine type epoxy resin and glycidylamine type epoxy resin, and tetrakisphenol ethane type epoxy. Examples thereof include resins and tetrafunctional epoxy resins such as glycidylamine type epoxy resins. Only one type of the epoxy resin may be used, or two or more types may be used in combination.
　また、上記樹脂粒子の材料としてエポキシ樹脂を用いる場合には、エポキシ樹脂とともに硬化剤を用いることが好ましい。上記硬化剤は、上記エポキシ樹脂を熱硬化させる。上記硬化剤は特に限定されない。上記硬化剤としては、イミダゾール硬化剤、アミン硬化剤、フェノール硬化剤、ポリチオール硬化剤等のチオール硬化剤、及び酸無水物硬化剤等が挙げられる。上記熱硬化剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。上記樹脂粒子の圧縮特性を好適な範囲に容易に制御する観点からは、上記硬化剤は、アミン硬化剤であることが好ましい。 When an epoxy resin is used as the material for the resin particles, it is preferable to use a curing agent together with the epoxy resin. The curing agent heat-cures the epoxy resin. The curing agent is not particularly limited. Examples of the curing agent include thiol curing agents such as imidazole curing agents, amine curing agents, phenol curing agents, and polythiol curing agents, and acid anhydride curing agents. Only one type of the thermosetting agent may be used, or two or more types may be used in combination. From the viewpoint of easily controlling the compression characteristics of the resin particles within a suitable range, the curing agent is preferably an amine curing agent.
　上記イミダゾール硬化剤は特に限定されない。上記イミダゾール硬化剤としては、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾリウムトリメリテート、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン及び２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４－ベンジル－５－ヒドロキシメチルイミダゾール、２－パラトルイル－４－メチル－５－ヒドロキシメチルイミダゾール、２－メタトルイル－４－メチル－５－ヒドロキシメチルイミダゾール、２－メタトルイル－４，５－ジヒドロキシメチルイミダゾール、２－パラトルイル－４，５－ジヒドロキシメチルイミダゾール等における１Ｈ－イミダゾールの５位の水素をヒドロキシメチル基で、かつ、２位の水素をフェニル基またはトルイル基で置換したイミダゾール化合物等が挙げられる。 The above imidazole curing agent is not particularly limited. Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimerite, and 2,4-diamino-6. -[2'-Methylimidazolyl- (1')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct , 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2-palatoryl-4-methyl-5 5th position of 1H-imidazole in -hydroxymethylimidazole, 2-methitolyl-4-methyl-5-hydroxymethylimidazole, 2-methitolyl-4,5-dihydroxymethylimidazole, 2-palatoryl-4,5-dihydroxymethylimidazole, etc. Examples thereof include an imidazole compound in which the hydrogen in the above is substituted with a hydroxymethyl group and the hydrogen at the 2-position is replaced with a phenyl group or a toluyl group.
　上記チオール硬化剤は特に限定されない。上記チオール硬化剤としては、トリメチロールプロパントリス－３－メルカプトプロピオネート、ペンタエリスリトールテトラキス－３－メルカプトプロピオネート及びジペンタエリスリトールヘキサ－３－メルカプトプロピオネート等が挙げられる。 The above thiol curing agent is not particularly limited. Examples of the thiol curing agent include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.
　上記アミン硬化剤は特に限定されない。上記アミン硬化剤としては、エチレンジアミン、ヘキサメチレンジアミン、オクタメチレンジアミン、デカメチレンジアミン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラスピロ［５．５］ウンデカン、ビス（４－アミノシクロヘキシル）メタン、ノルボルナンジアミン、フェニレンジアミン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノフェニルエーテル、メタキシレンジアミン、ジアミノナフタレン、ビスアミノメチルシクロヘキサン、及びジアミノジフェニルスルホン等が挙げられる。上記樹脂粒子の圧縮特性を好適な範囲に容易に制御する観点からは、上記アミン硬化剤は、エチレンジアミン、ヘキサメチレンジアミン、オクタメチレンジアミン、メタフェニレンジアミン、ジアミノジフェニルスルホン、フェニレンジアミン、又は２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパンであることが好ましい。上記樹脂粒子の圧縮特性を好適な範囲に容易に制御する観点からは、上記アミン硬化剤は、エチレンジアミン、ノルボルナンジアミン、ジアミノジフェニルメタン、フェニレンジアミン、又は２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパンであることがより好ましい。 The above amine curing agent is not particularly limited. Examples of the amine curing agent include ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane and bis. (4-Aminocyclohexyl) methane, norbornandiamine, phenylenediamine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, metaphenylenediamine, diaminodiphenylmethane, diaminophenyl ether, metaxylene diamine, diaminonaphthalene, Examples thereof include bisaminomethylcyclohexane and diaminodiphenylsulfone. From the viewpoint of easily controlling the compression characteristics of the resin particles within a suitable range, the amine curing agent is ethylenediamine, hexamethylenediamine, octamethylenediamine, metaphenylenediamine, diaminodiphenylsulfone, phenylenediamine, or 2,2. -Bis [4- (4-aminophenoxy) phenyl] propane is preferred. From the viewpoint of easily controlling the compression characteristics of the resin particles within a suitable range, the amine curing agent is ethylenediamine, norbornanediamine, diaminodiphenylmethane, phenylenediamine, or 2,2-bis [4- (4-aminophenoxy). ) Phenyl] Propane is more preferred.
　上記酸無水物硬化剤は特に限定されず、エポキシ化合物等の熱硬化性化合物の硬化剤として用いられる酸無水物であれば広く用いることができる。上記酸無水物硬化剤としては、無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルブテニルテトラヒドロ無水フタル酸、フタル酸誘導体の無水物、無水マレイン酸、無水ナジック酸、無水メチルナジック酸、無水グルタル酸、無水コハク酸、グリセリンビス無水トリメリット酸モノアセテート、及びエチレングリコールビス無水トリメリット酸等の２官能の酸無水物硬化剤、無水トリメリット酸等の３官能の酸無水物硬化剤、並びに、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、メチルシクロヘキセンテトラカルボン酸無水物、及びポリアゼライン酸無水物等の４官能以上の酸無水物硬化剤等が挙げられる。 The above-mentioned acid anhydride curing agent is not particularly limited, and any acid anhydride used as a curing agent for a thermosetting compound such as an epoxy compound can be widely used. Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylbutenyltetrahydrophthalic anhydride. Bifunctional such as phthalic acid derivative anhydride, maleic anhydride, nadic acid anhydride, methylnadic anhydride, glutaric anhydride, succinic anhydride, glycerinbis trimellitic anhydride monoacetate, and ethylene glycolbis trimellitic anhydride. Acid anhydride curing agent, trifunctional acid anhydride curing agent such as trimellitic anhydride, and pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, polyazelineic acid anhydride, etc. Examples thereof include an acid anhydride curing agent having four or more functions.
　上記樹脂粒子を、エチレン性不飽和基を有する重合性単量体を重合させて得る場合には、上記エチレン性不飽和基を有する重合性単量体としては、非架橋性の単量体と架橋性の単量体とが挙げられる。 When the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, the polymerizable monomer having an ethylenically unsaturated group is a non-crosslinkable monomer. Examples thereof include crosslinkable monomers.
　上記非架橋性の単量体としては、ビニル化合物として、スチレン、α－メチルスチレン、クロルスチレン等のスチレン単量体；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル等のビニルエーテル化合物；酢酸ビニル、酪酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル等の酸ビニルエステル化合物；塩化ビニル、フッ化ビニル等のハロゲン含有単量体；（メタ）アクリル化合物として、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート化合物；２－ヒドロキシエチル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリオキシエチレン（メタ）アクリレート、グリシジル（メタ）アクリレート等の酸素原子含有（メタ）アクリレート化合物；（メタ）アクリロニトリル等のニトリル含有単量体；トリフルオロメチル（メタ）アクリレート、ペンタフルオロエチル（メタ）アクリレート等のハロゲン含有（メタ）アクリレート化合物；α－オレフィン化合物として、ジイソブチレン、イソブチレン、リニアレン、エチレン、プロピレン等のオレフィン化合物；共役ジエン化合物として、イソプレン、ブタジエン等が挙げられる。 Examples of the non-crosslinkable monomer include styrene monomers such as styrene, α-methylstyrene and chlorostyrene; vinyl ether compounds such as methylvinyl ether, ethylvinyl ether and propylvinyl ether; vinyl acetate, vinyl butyrate, etc. Acid vinyl ester compounds such as vinyl laurate and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; as (meth) acrylic compounds, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and other alkyl ( Meta) acrylate compound; oxygen atom-containing (meth) acrylate compound such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate; (meth) acrylonitrile, etc. Nitrile-containing monomer; Halogen-containing (meth) acrylate compound such as trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate; olefins such as diisobutylene, isobutylene, linearene, ethylene and propylene as α-olefin compounds Compound; Examples of the conjugated diene compound include isoprene and butadiene.
　上記架橋性の単量体としては、ビニル化合物として、ジビニルベンゼン、１，４－ジビニロキシブタン、ジビニルスルホン等のビニル単量体；（メタ）アクリル化合物として、テトラメチロールメタンテトラ（メタ）アクリレート、ポリテトラメチレングリコールジアクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート等の多官能（メタ）アクリレート化合物；アリル化合物として、トリアリル（イソ）シアヌレート、トリアリルトリメリテート、ジアリルフタレート、ジアリルアクリルアミド、ジアリルエーテル；シラン化合物として、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、イソプロピルトリメトキシシラン、イソブチルトリメトキシシラン、シクロヘキシルトリメトキシシラン、ｎ－ヘキシルトリメトキシシラン、ｎ－オクチルトリエトキシシラン、ｎ－デシルトリメトキシシラン、フェニルトリメトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジイソプロピルジメトキシシラン、トリメトキシシリルスチレン、γ－（メタ）アクリロキシプロピルトリメトキシシラン、１，３－ジビニルテトラメチルジシロキサン、メチルフェニルジメトキシシラン、ジフェニルジメトキシシラン等のシランアルコキシド化合物；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ジメトキシメチルビニルシシラン、ジメトキシエチルビニルシラン、ジエトキシメチルビニルシラン、ジエトキシエチルビニルシラン、エチルメチルジビニルシラン、メチルビニルジメトキシシラン、エチルビニルジメトキシシラン、メチルビニルジエトキシシラン、エチルビニルジエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン等の重合性二重結合含有シランアルコキシド；デカメチルシクロペンタシロキサン等の環状シロキサン；片末端変性シリコーンオイル、両末端シリコーンオイル、側鎖型シリコーンオイル等の変性（反応性）シリコーンオイル；（メタ）アクリル酸、マレイン酸、無水マレイン酸等のカルボキシル基含有単量体等が挙げられる。 Examples of the crosslinkable monomer include vinyl monomers such as divinylbenzene, 1,4-dibinyloxybutane, and divinylsulfone as vinyl compounds; and tetramethylolmethanetetra (meth) acrylate as (meth) acrylic compounds. , Polytetramethylene glycol diacrylate, Tetramethylolmethanetri (meth) acrylate, Tetramethylolmethanedi (meth) acrylate, Trimethylolpropanetri (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) ) Acrylic, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di Polyfunctional (meth) acrylate compounds such as (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate; As allyl compounds, triallyl (iso) cyanurate, triallyl trimerite, diallyl phthalate, diallylacrylamide, diallyl ether; as silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxy Silane alkoxides such as silane, dimethyldiethoxysilane, diisopropyldimethoxysilane, trimethoxysilylstyrene, γ- (meth) acryloxipropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, diphenyldimethoxysilane Compounds; Vinyltrimethoxysilane, Vinyltriethoxysilane, Dimethoxymethylvinylsisilane, Dimethoxyethylvinylsilane, Diethoxymethylvinylsilane, Diethoxyethylvinylsilane, Ethylmethyldivinylsilane, Methylvinyldimethoxysilane, Ethyl Vinyldimethoxysilane, methylvinyldiethoxysilane, ethylvinyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-Methyloxypropyltriethoxysilane, 3-Acryloxipropyltrimethoxysilane and other polymerizable double bond-containing silane alkoxides; Cyclic siloxanes such as decamethylcyclopentasiloxane; One-ended modified silicone oil, Double-ended silicone oil, Modified (reactive) silicone oils such as side chain type silicone oils; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride can be mentioned.
　上記樹脂粒子は、上記エチレン性不飽和基を有する重合性単量体を重合させることによって得ることができる。上記の重合方法としては特に限定されず、ラジカル重合、イオン重合、重縮合（縮合重合、縮重合）、付加縮合、リビング重合、及びリビングラジカル重合等の公知の方法が挙げられる。また、他の重合方法としては、ラジカル重合開始剤の存在下での懸濁重合が挙げられる。 The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group. The above-mentioned polymerization method is not particularly limited, and examples thereof include known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, polycondensation polymerization), addition condensation, living polymerization, and living radical polymerization. Further, as another polymerization method, suspension polymerization in the presence of a radical polymerization initiator can be mentioned.
　（導電性粒子）
　上記導電性粒子は、上述した樹脂粒子と、上記樹脂粒子の表面上に配置された導電部とを備える。 (Conductive particles)
The conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles.
　図２は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。 FIG. 2 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
　図２に示す導電性粒子１１は、樹脂粒子１と、樹脂粒子１の表面上に配置された導電部２とを有する。導電部２は、樹脂粒子１の表面を被覆している。導電性粒子１１は、樹脂粒子１の表面が導電部２により被覆された被覆粒子である。 The conductive particles 11 shown in FIG. 2 have a resin particle 1 and a conductive portion 2 arranged on the surface of the resin particle 1. The conductive portion 2 covers the surface of the resin particles 1. The conductive particles 11 are coated particles in which the surface of the resin particles 1 is coated with the conductive portion 2.
　図３は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。 FIG. 3 is a cross-sectional view showing the conductive particles according to the second embodiment of the present invention.
　図３に示す導電性粒子２１は、樹脂粒子１と、樹脂粒子１の表面上に配置された導電部２２とを有する。図３に示す導電性粒子２１では、導電部２２のみが、図２に示す導電性粒子１１と異なる。導電部２２は、内層である第１の導電部２２Ａと外層である第２の導電部２２Ｂとを有する。樹脂粒子１の表面上に、第１の導電部２２Ａが配置されている。第１の導電部２２Ａの表面上に、第２の導電部２２Ｂが配置されている。 The conductive particles 21 shown in FIG. 3 have a resin particle 1 and a conductive portion 22 arranged on the surface of the resin particle 1. In the conductive particles 21 shown in FIG. 3, only the conductive portion 22 is different from the conductive particles 11 shown in FIG. The conductive portion 22 has a first conductive portion 22A which is an inner layer and a second conductive portion 22B which is an outer layer. The first conductive portion 22A is arranged on the surface of the resin particles 1. The second conductive portion 22B is arranged on the surface of the first conductive portion 22A.
　図４は、本発明の第３の実施形態に係る導電性粒子を示す断面図である。 FIG. 4 is a cross-sectional view showing the conductive particles according to the third embodiment of the present invention.
　図４に示す導電性粒子３１は、樹脂粒子１と、導電部３２と、複数の芯物質３３と、複数の絶縁性物質３４とを有する。 The conductive particle 31 shown in FIG. 4 has a resin particle 1, a conductive portion 32, a plurality of core substances 33, and a plurality of insulating substances 34.
　導電部３２は、樹脂粒子１の表面上に配置されている。導電性粒子３１は導電性の表面に、複数の突起３１ａを有する。導電部３２は外表面に、複数の突起３２ａを有する。このように、上記導電性粒子は、導電性粒子の導電性の表面に突起を有していてもよく、導電部の外表面に突起を有していてもよい。複数の芯物質３３が、樹脂粒子１の表面上に配置されている。複数の芯物質３３は導電部３２内に埋め込まれている。芯物質３３は、突起３１ａ，３２ａの内側に配置されている。導電部３２は、複数の芯物質３３を被覆している。複数の芯物質３３により導電部３２の外表面が隆起されており、突起３１ａ，３２ａが形成されている。 The conductive portion 32 is arranged on the surface of the resin particles 1. The conductive particles 31 have a plurality of protrusions 31a on the conductive surface. The conductive portion 32 has a plurality of protrusions 32a on the outer surface. As described above, the conductive particles may have protrusions on the conductive surface of the conductive particles, or may have protrusions on the outer surface of the conductive portion. A plurality of core substances 33 are arranged on the surface of the resin particles 1. The plurality of core substances 33 are embedded in the conductive portion 32. The core material 33 is arranged inside the protrusions 31a and 32a. The conductive portion 32 covers a plurality of core substances 33. The outer surface of the conductive portion 32 is raised by the plurality of core substances 33, and protrusions 31a and 32a are formed.
　導電性粒子３１は、導電部３２の外表面上に配置された絶縁性物質３４を有する。導電部３２の外表面の少なくとも一部の領域が、絶縁性物質３４により被覆されている。絶縁性物質３４は絶縁性を有する材料により形成されており、絶縁性粒子である。このように、上記導電性粒子は、導電部の外表面上に配置された絶縁性物質を有していてもよい。 The conductive particles 31 have an insulating substance 34 arranged on the outer surface of the conductive portion 32. At least a part of the outer surface of the conductive portion 32 is covered with the insulating substance 34. The insulating substance 34 is formed of an insulating material and is an insulating particle. As described above, the conductive particles may have an insulating substance arranged on the outer surface of the conductive portion.
　上記導電部を形成するための金属は特に限定されない。上記金属としては、金、銀、パラジウム、銅、白金、亜鉛、鉄、錫、鉛、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、タリウム、ゲルマニウム、カドミウム、ケイ素、タングステン、モリブデン及びこれらの合金等が挙げられる。また、上記金属としては、錫ドープ酸化インジウム（ＩＴＯ）及びはんだ等が挙げられる。電極間の接続信頼性をより一層高める観点からは、上記金属は、錫を含む合金、ニッケル、パラジウム、銅又は金であることが好ましく、ニッケル又はパラジウムであることが好ましい。 The metal for forming the conductive portion is not particularly limited. Examples of the metals include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, tarium, germanium, cadmium, silicon, tungsten and molybdenum. And these alloys and the like. Examples of the metal include tin-doped indium oxide (ITO) and solder. From the viewpoint of further enhancing the connection reliability between the electrodes, the metal is preferably a tin-containing alloy, nickel, palladium, copper or gold, and preferably nickel or palladium.
　導電性粒子１１，３１のように、上記導電部は、１つの層により形成されていてもよい。導電性粒子２１のように、上記導電部は、複数の層により形成されていてもよい。すなわち、上記導電部は、２層以上の積層構造を有していてもよい。導電部が複数の層により形成されている場合には、最外層は、金層、ニッケル層、パラジウム層、銅層又は錫と銀とを含む合金層であることが好ましく、金層であることがより好ましい。最外層がこれらの好ましい導電部である場合には、電極間の接続信頼性をより一層高めることができる。また、最外層が金層である場合には、耐腐食性をより一層高めることができる。 The conductive portion may be formed of one layer, such as the conductive particles 11 and 31. Like the conductive particles 21, the conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers. When the conductive portion is formed by a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer or an alloy layer containing tin and silver, and is preferably a gold layer. Is more preferable. When the outermost layer is these preferable conductive portions, the connection reliability between the electrodes can be further enhanced. Further, when the outermost layer is a gold layer, the corrosion resistance can be further improved.
　上記樹脂粒子の表面上に導電部を形成する方法は特に限定されない。上記導電部を形成する方法としては、無電解めっきによる方法、電気めっきによる方法、物理的蒸着による方法、並びに金属粉末もしくは金属粉末とバインダーとを含むペーストを樹脂粒子の表面にコーティングする方法等が挙げられる。導電部をより一層容易に形成する観点からは、無電解めっきによる方法が好ましい。上記物理的蒸着による方法としては、真空蒸着、イオンプレーティング及びイオンスパッタリング等の方法が挙げられる。 The method of forming the conductive portion on the surface of the resin particles is not particularly limited. Examples of the method for forming the conductive portion include a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating a metal powder or a paste containing a metal powder and a binder on the surface of resin particles. Can be mentioned. From the viewpoint of forming the conductive portion more easily, the method by electroless plating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
　上記導電性粒子を１０％圧縮したときの圧縮弾性率（１０％Ｋ値）は、好ましくは１０００Ｎ／ｍｍ２以上、より好ましくは３０００Ｎ／ｍｍ２以上、更に好ましくは４５００Ｎ／ｍｍ２以上、好ましくは１００００Ｎ／ｍｍ２以下、より好ましくは９０００Ｎ／ｍｍ２以下、更に好ましくは８０００Ｎ／ｍｍ２以下である。上記１０％Ｋ値が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 Compression modulus when the conductive particles are compressed 10% (10% K value), preferably 1000 N / mm 2 or more, more preferably 3000N / mm 2 or more, more preferably 4500N / mm 2 or more, preferably 10000 N / mm 2 or less, more preferably 9000 N / mm 2, more preferably not more than 8000 N / mm 2. When the 10% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記導電性粒子を３０％圧縮したときの圧縮弾性率（３０％Ｋ値）は、好ましくは１０００Ｎ／ｍｍ２以上、より好ましくは３０００Ｎ／ｍｍ２以上、更に好ましくは４５００Ｎ／ｍｍ２以上、好ましくは１００００Ｎ／ｍｍ２以下、より好ましくは８０００Ｎ／ｍｍ２以下、更に好ましくは６０００Ｎ／ｍｍ２以下である。上記３０％Ｋ値が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The conductive compressive modulus when particles were compressed 30% (30% K value), preferably 1000 N / mm 2 or more, more preferably 3000N / mm 2 or more, more preferably 4500N / mm 2 or more, preferably 10000 N / mm 2 or less, more preferably 8000 N / mm 2, more preferably not more than 6000 N / mm 2. When the 30% K value is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記導電性粒子における上記圧縮弾性率（１０％Ｋ値及び３０％Ｋ値）は、上記樹脂粒子における上記圧縮弾性率（１０％Ｋ値及び３０％Ｋ値）と同様にして測定できる。 The compressive elastic modulus (10% K value and 30% K value) of the conductive particles can be measured in the same manner as the compressive elastic modulus (10% K value and 30% K value) of the resin particles.
　上記圧縮弾性率は、導電性粒子の硬さを普遍的かつ定量的に表す。上記圧縮弾性率の使用により、導電性粒子の硬さを定量的かつ一義的に表すことができる。 The compressive elastic modulus universally and quantitatively represents the hardness of conductive particles. By using the compressive elastic modulus, the hardness of the conductive particles can be expressed quantitatively and uniquely.
　上記導電性粒子の圧縮回復率は、好ましくは５％以上、より好ましくは８％以上であり、好ましくは６０％以下、より好ましくは４０％以下である。上記圧縮回復率が上記下限以上及び上記上限以下であると、本発明の効果をより一層効果的に発揮することができる。 The compression recovery rate of the conductive particles is preferably 5% or more, more preferably 8% or more, preferably 60% or less, and more preferably 40% or less. When the compression recovery rate is at least the above lower limit and at least the above upper limit, the effect of the present invention can be exhibited even more effectively.
　上記導電性粒子の上記圧縮回復率は、上記樹脂粒子における上記圧縮回復率と同様にして測定できる。 The compression recovery rate of the conductive particles can be measured in the same manner as the compression recovery rate of the resin particles.
　上記導電性粒子の粒子径は、好ましくは０．５μｍ以上、より好ましくは１．０μｍ以上であり、好ましくは５００μｍ以下、より好ましくは４５０μｍ以下、より一層好ましくは１００μｍ以下、さらに好ましくは５０μｍ以下、特に好ましくは２０μｍ以下である。上記導電性粒子の粒子径が上記下限以上及び上記上限以下であると、導電性粒子を用いて電極間を接続した場合に、導電性粒子と電極との接触面積が十分に大きくなり、かつ導電部を形成する際に凝集した導電性粒子が形成され難くなる。また、導電性粒子を介して接続された電極間の間隔が大きくなりすぎず、かつ導電部が樹脂粒子の表面から剥離し難くなる。また、上記導電性粒子の粒子径が上記下限以上及び上記上限以下であると、導電性粒子を導電材料の用途に好適に用いることができる。 The particle size of the conductive particles is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 500 μm or less, more preferably 450 μm or less, still more preferably 100 μm or less, still more preferably 50 μm or less. Especially preferably, it is 20 μm or less. When the particle diameter of the conductive particles is equal to or greater than the above lower limit and equal to or less than the above upper limit, the contact area between the conductive particles and the electrodes becomes sufficiently large when the electrodes are connected using the conductive particles, and the conductivity is increased. It becomes difficult to form agglomerated conductive particles when forming the portion. In addition, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive portion does not easily peel off from the surface of the resin particles. Further, when the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of the conductive material.
　上記導電性粒子の粒子径は、導電性粒子が真球状である場合には直径を意味し、導電性粒子が真球状以外の形状である場合には、その体積相当の真球と仮定した際の直径を意味する。 The particle diameter of the conductive particles means the diameter when the conductive particles are spherical, and when the conductive particles have a shape other than spherical, it is assumed to be a true sphere corresponding to the volume. Means the diameter of.
　上記導電性粒子の粒子径は、平均粒子径であることが好ましく、数平均粒子径であることがより好ましい。上記導電性粒子の粒子径は、任意の導電性粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することや、レーザー回折式粒度分布測定を行うことにより求められる。電子顕微鏡又は光学顕微鏡での観察では、１個当たりの導電性粒子の粒子径は、円相当径での粒子径として求められる。電子顕微鏡又は光学顕微鏡での観察において、任意の５０個の導電性粒子の円相当径での平均粒子径は、球相当径での平均粒子径とほぼ等しくなる。レーザー回折式粒度分布測定では、１個当たりの導電性粒子の粒子径は、球相当径での粒子径として求められる。上記導電性粒子の粒子径は、レーザー回折式粒度分布測定により算出することが好ましい。 The particle size of the conductive particles is preferably an average particle size, and more preferably a number average particle size. The particle size of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or performing a laser diffraction type particle size distribution measurement. In observation with an electron microscope or an optical microscope, the particle size of each conductive particle is determined as the particle size in the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 conductive particles in the circle equivalent diameter is substantially equal to the average particle diameter in the sphere equivalent diameter. In the laser diffraction type particle size distribution measurement, the particle size of each conductive particle is determined as the particle size in the equivalent sphere diameter. The particle size of the conductive particles is preferably calculated by laser diffraction type particle size distribution measurement.
　上記導電部の厚みは、好ましくは０．００５μｍ以上、より好ましくは０．０１μｍ以上であり、好ましくは１０μｍ以下、より好ましくは１μｍ以下、さらに好ましくは０．３μｍ以下である。上記導電部の厚みは、導電部が多層である場合には導電部全体の厚みである。上記導電部の厚みが上記下限以上及び上記上限以下であると、十分な導電性が得られ、かつ導電性粒子が硬くなりすぎずに、電極間の接続の際に導電性粒子が十分に変形する。 The thickness of the conductive portion is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, still more preferably 0.3 μm or less. The thickness of the conductive portion is the thickness of the entire conductive portion when the conductive portion has multiple layers. When the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not too hard and the conductive particles are sufficiently deformed at the time of connection between the electrodes. To do.
　上記導電部が複数の層により形成されている場合に、最外層の導電部の厚みは、好ましくは０．００１μｍ以上、より好ましくは０．０１μｍ以上であり、好ましくは０．５μｍ以下、より好ましくは０．１μｍ以下である。上記最外層の導電部の厚みが上記下限以上及び上記上限以下であると、最外層の導電部による被覆が均一になり、耐腐食性が十分に高くなり、かつ電極間の接続信頼性をより一層高めることができる。また、上記最外層が金層である場合に、金層の厚みが薄いほど、コストが低くなる。 When the conductive portion is formed of a plurality of layers, the thickness of the conductive portion of the outermost layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably. Is 0.1 μm or less. When the thickness of the conductive portion of the outermost layer is equal to or higher than the lower limit and lower than the upper limit, the coating by the conductive portion of the outermost layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection reliability between the electrodes becomes higher. It can be further enhanced. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.
　上記導電部の厚みは、例えば透過型電子顕微鏡（ＴＥＭ）を用いて、導電性粒子の断面を観察することにより測定できる。上記導電部の厚みについては、任意の導電部の厚み５箇所の平均値を１個の導電性粒子の導電部の厚みとして算出することが好ましく、導電部全体の厚みの平均値を１個の導電性粒子の導電部の厚みとして算出することがより好ましい。上記導電部の厚みは、任意の導電性粒子５０個について、各導電性粒子の導電部の厚みの平均値を算出することにより求めることが好ましい。 The thickness of the conductive portion can be measured by observing the cross section of the conductive particles, for example, using a transmission electron microscope (TEM). Regarding the thickness of the conductive portion, it is preferable to calculate the average value of the thickness of any of the conductive portions at five points as the thickness of the conductive portion of one conductive particle, and the average value of the thickness of the entire conductive portion is one. It is more preferable to calculate as the thickness of the conductive portion of the conductive particles. The thickness of the conductive portion is preferably obtained by calculating the average value of the thickness of the conductive portion of each conductive particle for 50 arbitrary conductive particles.
　上記導電性粒子は、導電部の外表面に突起を有することが好ましい。上記導電性粒子は、導電性の表面に突起を有することが好ましい。上記突起は複数であることが好ましい。導電部の表面並びに導電性粒子により接続される電極の表面には、酸化被膜が形成されていることが多い。突起を有する導電性粒子を用いた場合には、電極間に導電性粒子を配置して圧着させることにより、突起により上記酸化被膜が効果的に排除される。このため、電極と導電性粒子の導電部とをより一層確実に接触させることができ、電極間の接続抵抗をより一層低くすることができる。さらに、導電性粒子が表面に絶縁性物質を備える場合に、又は導電性粒子がバインダー樹脂中に分散されて導電材料として用いられる場合に、導電性粒子の突起によって、導電性粒子と電極との間の絶縁性物質又はバインダー樹脂をより一層効果的に排除できる。このため、電極間の接続信頼性をより一層高めることができる。 It is preferable that the conductive particles have protrusions on the outer surface of the conductive portion. The conductive particles preferably have protrusions on the conductive surface. It is preferable that the number of the protrusions is plurality. An oxide film is often formed on the surface of the conductive portion and the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively removed by the protrusions by arranging the conductive particles between the electrodes and crimping them. Therefore, the electrodes and the conductive portions of the conductive particles can be brought into contact with each other more reliably, and the connection resistance between the electrodes can be further reduced. Further, when the conductive particles have an insulating substance on the surface, or when the conductive particles are dispersed in the binder resin and used as a conductive material, the protrusions of the conductive particles cause the conductive particles to be connected to the electrode. The insulating substance or binder resin between them can be eliminated more effectively. Therefore, the connection reliability between the electrodes can be further improved.
　上記導電性粒子の表面に突起を形成する方法としては、樹脂粒子の表面に芯物質を付着させた後、無電解めっきにより導電部を形成する方法、及び樹脂粒子の表面に無電解めっきにより導電部を形成した後、芯物質を付着させ、さらに無電解めっきにより導電部を形成する方法等が挙げられる。また、突起を形成するために、上記芯物質を用いなくてもよい。 As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive portion by electroless plating after adhering a core material to the surface of the resin particles, and a method of forming a conductive portion on the surface of the resin particles by electroless plating. Examples thereof include a method in which a core material is attached after forming the portion, and then a conductive portion is formed by electroless plating. Further, it is not necessary to use the core substance in order to form the protrusions.
　上記突起を形成する方法としては、以下の方法等も挙げられる。樹脂粒子の表面に無電解めっきにより導電部を形成する途中段階で芯物質を添加する方法。無電解めっきにより芯物質を用いずに突起を形成する方法として、無電解めっきにより金属核を発生させ、樹脂粒子又は導電部の表面に金属核を付着させ、さらに無電解めっきにより導電部を形成する方法。 Examples of the method for forming the protrusions include the following methods. A method of adding a core substance in the middle of forming a conductive part by electroless plating on the surface of resin particles. As a method of forming protrusions by electroless plating without using a core substance, metal nuclei are generated by electroless plating, metal nuclei are attached to the surface of resin particles or conductive parts, and the conductive parts are further formed by electroless plating. how to.
　上記導電性粒子は、上記導電部の外表面上に配置された絶縁性物質をさらに備えることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡を防止できる。具体的には、複数の導電性粒子が接触したときに、複数の電極間に絶縁性物質が存在するので、上下の電極間ではなく横方向に隣り合う電極間の短絡を防止することができる。なお、電極間の接続の際に、２つの電極で導電性粒子を加圧することにより、導電性粒子の導電部と電極との間の絶縁性物質を容易に排除できる。導電性粒子が上記導電部の表面に突起を有する場合には、導電性粒子の導電部と電極との間の絶縁性物質をより一層容易に排除できる。上記絶縁性物質は、絶縁性樹脂層又は絶縁性粒子であることが好ましく、絶縁性粒子であることがより好ましい。上記絶縁性粒子は、絶縁性樹脂粒子であることが好ましい。 It is preferable that the conductive particles further include an insulating substance arranged on the outer surface of the conductive portion. In this case, if conductive particles are used for the connection between the electrodes, a short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles come into contact with each other, an insulating substance exists between the plurality of electrodes, so that it is possible to prevent a short circuit between the electrodes adjacent to each other in the lateral direction instead of between the upper and lower electrodes. .. By pressurizing the conductive particles with the two electrodes at the time of connection between the electrodes, the insulating substance between the conductive portion of the conductive particles and the electrodes can be easily removed. When the conductive particles have protrusions on the surface of the conductive portion, the insulating substance between the conductive portion of the conductive particles and the electrode can be more easily removed. The insulating substance is preferably an insulating resin layer or insulating particles, and more preferably insulating particles. The insulating particles are preferably insulating resin particles.
　上記導電部の外表面、及び絶縁性粒子の表面はそれぞれ、反応性官能基を有する化合物によって被覆されていてもよい。導電部の外表面と絶縁性粒子の表面とは、直接化学結合していなくてもよく、反応性官能基を有する化合物によって間接的に化学結合していてもよい。導電部の外表面にカルボキシル基を導入した後、該カルボキシル基がポリエチレンイミン等の高分子電解質を介して絶縁性粒子の表面の官能基と化学結合していてもよい。 The outer surface of the conductive portion and the surface of the insulating particles may each be coated with a compound having a reactive functional group. The outer surface of the conductive portion and the surface of the insulating particles may not be directly chemically bonded, or may be indirectly chemically bonded by a compound having a reactive functional group. After introducing a carboxyl group into the outer surface of the conductive portion, the carboxyl group may be chemically bonded to a functional group on the surface of the insulating particles via a polymer electrolyte such as polyethyleneimine.
　（導電材料）
　上記導電材料は、上述した導電性粒子と、バインダー樹脂とを含む。上記導電性粒子は、バインダー樹脂中に分散され、導電材料として用いられることが好ましい。上記導電材料は、異方性導電材料であることが好ましい。上記導電材料は、電極の電気的な接続に好適に用いられる。上記導電材料は、回路接続材料であることが好ましい。 (Conductive material)
The conductive material includes the above-mentioned conductive particles and a binder resin. The conductive particles are preferably dispersed in the binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive material is preferably used for electrical connection of electrodes. The conductive material is preferably a circuit connection material.
　上記バインダー樹脂は特に限定されない。上記バインダー樹脂として、公知の絶縁性の樹脂が用いられる。上記バインダー樹脂は、熱可塑性成分（熱可塑性化合物）又は硬化性成分を含むことが好ましく、硬化性成分を含むことがより好ましい。上記硬化性成分としては、光硬化性成分及び熱硬化性成分が挙げられる。上記光硬化性成分は、光硬化性化合物及び光重合開始剤を含むことが好ましい。上記熱硬化性成分は、熱硬化性化合物及び熱硬化剤を含むことが好ましい。上記バインダー樹脂としては、例えば、ビニル樹脂、熱可塑性樹脂、硬化性樹脂、熱可塑性ブロック共重合体及びエラストマー等が挙げられる。上記バインダー樹脂は、１種のみが用いられてもよく、２種以上が併用されてもよい。 The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. The binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component. Examples of the curable component include a photocurable component and a thermosetting component. The photocurable component preferably contains a photocurable compound and a photopolymerization initiator. The thermosetting component preferably contains a thermosetting compound and a thermosetting agent. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. Only one kind of the binder resin may be used, or two or more kinds may be used in combination.
　上記ビニル樹脂としては、例えば、酢酸ビニル樹脂、アクリル樹脂及びスチレン樹脂等が挙げられる。上記熱可塑性樹脂としては、例えば、ポリオレフィン樹脂、エチレン－酢酸ビニル共重合体及びポリアミド樹脂等が挙げられる。上記硬化性樹脂としては、例えば、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂及び不飽和ポリエステル樹脂等が挙げられる。なお、上記硬化性樹脂は、常温硬化型樹脂、熱硬化型樹脂、光硬化型樹脂又は湿気硬化型樹脂であってもよい。上記硬化性樹脂は、硬化剤と併用されてもよい。上記熱可塑性ブロック共重合体としては、例えば、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物、及びスチレン－イソプレン－スチレンブロック共重合体の水素添加物等が挙げられる。上記エラストマーとしては、例えば、スチレン－ブタジエン共重合ゴム、及びアクリロニトリル－スチレンブロック共重合ゴム等が挙げられる。 Examples of the vinyl resin include vinyl acetate resin, acrylic resin, styrene resin and the like. Examples of the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins. Examples of the curable resin include epoxy resin, urethane resin, polyimide resin, unsaturated polyester resin and the like. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated additive of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogen additives for styrene block copolymers and the like can be mentioned. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
　上記導電材料は、上記導電性粒子及び上記バインダー樹脂の他に、例えば、充填剤、増量剤、軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤及び難燃剤等の各種添加剤を含んでいてもよい。 In addition to the conductive particles and the binder resin, the conductive material includes, for example, a filler, a bulking agent, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a photostabilizer. It may contain various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant.
　上記バインダー樹脂中に上記導電性粒子を分散させる方法は、従来公知の分散方法を用いることができ特に限定されない。上記バインダー樹脂中に上記導電性粒子を分散させる方法としては、例えば、以下の方法等が挙げられる。上記バインダー樹脂中に上記導電性粒子を添加した後、プラネタリーミキサー等で混練して分散させる方法。上記導電性粒子を水又は有機溶剤中にホモジナイザー等を用いて均一に分散させた後、上記バインダー樹脂中に添加し、プラネタリーミキサー等で混練して分散させる方法。上記バインダー樹脂を水又は有機溶剤等で希釈した後、上記導電性粒子を添加し、プラネタリーミキサー等で混練して分散させる方法。 The method for dispersing the conductive particles in the binder resin is not particularly limited as a conventionally known dispersion method can be used. Examples of the method for dispersing the conductive particles in the binder resin include the following methods. A method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. A method in which the conductive particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, added to the binder resin, and kneaded and dispersed by a planetary mixer or the like. A method in which the binder resin is diluted with water, an organic solvent or the like, the conductive particles are added, and the binder resin is kneaded and dispersed with a planetary mixer or the like.
　上記導電材料の２５℃での粘度（η２５）は、好ましくは３０Ｐａ・ｓ以上、より好ましくは５０Ｐａ・ｓ以上であり、好ましくは４００Ｐａ・ｓ以下、より好ましくは３００Ｐａ・ｓ以下である。上記導電材料の２５℃での粘度が上記下限以上及び上記上限以下であると、電極間の接続信頼性をより一層効果的に高めることができる。上記粘度（η２５）は、配合成分の種類及び配合量により適宜調整することができる。 The viscosity (η25) of the conductive material at 25 ° C. is preferably 30 Pa · s or more, more preferably 50 Pa · s or more, preferably 400 Pa · s or less, and more preferably 300 Pa · s or less. When the viscosity of the conductive material at 25 ° C. is at least the above lower limit and at least the above upper limit, the connection reliability between the electrodes can be further effectively improved. The viscosity (η25) can be appropriately adjusted depending on the type and amount of the compounding components.
　上記粘度（η２５）は、例えば、Ｅ型粘度計（東機産業社製「ＴＶＥ２２Ｌ」）等を用いて、２５℃及び５ｒｐｍの条件で測定することができる。 The viscosity (η25) can be measured at 25 ° C. and 5 rpm using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.).
　上記導電材料は、導電ペースト及び導電フィルム等として使用され得る。本発明に係る導電材料が、導電フィルムである場合には、導電性粒子を含む導電フィルムに、導電性粒子を含まないフィルムが積層されていてもよい。上記導電ペーストは異方性導電ペーストであることが好ましい。上記導電フィルムは異方性導電フィルムであることが好ましい。 The conductive material can be used as a conductive paste, a conductive film, or the like. When the conductive material according to the present invention is a conductive film, a film containing no conductive particles may be laminated on the conductive film containing the conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.
　上記導電材料１００重量％中、上記バインダー樹脂の含有量は、好ましくは１０重量％以上、より好ましくは３０重量％以上、さらに好ましくは５０重量％以上、特に好ましくは７０重量％以上であり、好ましくは９９．９９重量％以下、より好ましくは９９．９重量％以下である。上記バインダー樹脂の含有量が上記下限以上及び上記上限以下であると、電極間に導電性粒子が効率的に配置され、導電材料により接続された接続対象部材の接続信頼性がより一層高くなる。 The content of the binder resin in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more. Is 99.99% by weight or less, more preferably 99.9% by weight or less. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further improved.
　上記導電材料１００重量％中、上記導電性粒子の含有量は、好ましくは０．０１重量％以上、より好ましくは０．１重量％以上であり、好ましくは８０重量％以下、より好ましくは６０重量％以下、より一層好ましくは４０重量％以下、さらに好ましくは２０重量％以下、特に好ましくは１０重量％以下である。上記導電性粒子の含有量が上記下限以上及び上記上限以下であると、電極間の接続抵抗をより一層効果的に低くすることができ、かつ、電極間の接続信頼性をより一層効果的に高めることができる。 The content of the conductive particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. % Or less, still more preferably 40% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be further effectively lowered, and the connection reliability between the electrodes can be further effectively reduced. Can be enhanced.
　（接続構造体）
　上述した樹脂粒子を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。 (Connection structure)
A connection structure can be obtained by connecting the members to be connected using the resin particles described above.
　上記樹脂粒子を用いた上記接続構造体は、第１の接続対象部材と、第２の接続対象部材と、上記第１の接続対象部材と上記第２の接続対象部材とを接続している接続部とを備える。上記接続構造体では、上記接続部が、上記樹脂粒子により形成されているか、又は上記樹脂粒子を含む組成物により形成されている。上記樹脂粒子を用いた上記接続構造体では、上記樹脂粒子は、上記第１の接続対象部材と上記第２の接続対象部材とに直接接していることが好ましい。 The connection structure using the resin particles connects the first connection target member, the second connection target member, the first connection target member, and the second connection target member. It has a part. In the connection structure, the connection portion is formed of the resin particles or a composition containing the resin particles. In the connection structure using the resin particles, it is preferable that the resin particles are in direct contact with the first connection target member and the second connection target member.
　上述した導電性粒子、又は上述した導電性粒子とバインダー樹脂とを含む導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。 A connection structure can be obtained by connecting the members to be connected using the above-mentioned conductive particles or a conductive material containing the above-mentioned conductive particles and a binder resin.
　上記導電性粒子を用いた上記接続構造体は、第１の電極を表面に有する第１の接続対象部材と、第２の電極を表面に有する第２の接続対象部材と、上記第１の接続対象部材と上記第２の接続対象部材とを接続している接続部とを備える。上記接続構造体では、上記接続部が、導電性粒子により形成されているか、又は上記導電性粒子とバインダー樹脂とを含む導電材料により形成されている。上記導電性粒子は、上述した樹脂粒子と、上記樹脂粒子の表面上に配置された導電部とを備える。上記接続構造体では、上記第１の電極と上記第２の電極とが上記導電性粒子により電気的に接続されている。 The connection structure using the conductive particles includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, and the first connection. It includes a connecting portion that connects the target member and the second connection target member. In the connection structure, the connection portion is formed of conductive particles or is formed of a conductive material containing the conductive particles and a binder resin. The conductive particles include the above-mentioned resin particles and a conductive portion arranged on the surface of the resin particles. In the connection structure, the first electrode and the second electrode are electrically connected by the conductive particles.
　上記導電性粒子が単独で用いられた場合には、接続部自体が導電性粒子である。即ち、上記第１の接続対象部材と上記第２の接続対象部材とが上記導電性粒子により接続される。上記接続構造体を得るために用いられる上記導電材料は、異方性導電材料であることが好ましい。 When the above conductive particles are used alone, the connecting portion itself is a conductive particle. That is, the first connection target member and the second connection target member are connected by the conductive particles. The conductive material used to obtain the connection structure is preferably an anisotropic conductive material.
　図５は、本発明の第１の実施形態に係る導電性粒子を用いた接続構造体の一例を示す断面図である。 FIG. 5 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention.
　図５に示す接続構造体４１は、第１の接続対象部材４２と、第２の接続対象部材４３と、第１の接続対象部材４２と第２の接続対象部材４３とを接続している接続部４４とを備える。接続部４４は、導電性粒子１１とバインダー樹脂とを含む導電材料により形成されている。図５では、図示の便宜上、導電性粒子１１は略図的に示されている。導電性粒子１１にかえて、導電性粒子２１，３１の他の導電性粒子を用いてもよい。 The connection structure 41 shown in FIG. 5 is a connection connecting the first connection target member 42, the second connection target member 43, the first connection target member 42, and the second connection target member 43. A unit 44 is provided. The connecting portion 44 is formed of a conductive material containing the conductive particles 11 and the binder resin. In FIG. 5, for convenience of illustration, the conductive particles 11 are shown schematically. Instead of the conductive particles 11, other conductive particles 21 and 31 may be used.
　第１の接続対象部材４２は表面（上面）に、複数の第１の電極４２ａを有する。第２の接続対象部材４３は表面（下面）に、複数の第２の電極４３ａを有する。第１の電極４２ａと第２の電極４３ａとが、１つ又は複数の導電性粒子１１により電気的に接続されている。従って、第１，第２の接続対象部材４２，４３が導電性粒子１１により電気的に接続されている。 The first connection target member 42 has a plurality of first electrodes 42a on the surface (upper surface). The second connection target member 43 has a plurality of second electrodes 43a on the surface (lower surface). The first electrode 42a and the second electrode 43a are electrically connected by one or more conductive particles 11. Therefore, the first and second connection target members 42 and 43 are electrically connected by the conductive particles 11.
　上記接続構造体の製造方法は特に限定されない。接続構造体の製造方法の一例としては、第１の接続対象部材と第２の接続対象部材との間に上記導電材料を配置し、積層体を得た後、該積層体を加熱及び加圧する方法等が挙げられる。上記加圧時の圧力は、好ましくは４０ＭＰａ以上、より好ましくは６０ＭＰａ以上であり、好ましくは９０ＭＰａ以下、より好ましくは７０ＭＰａ以下である。上記加熱時の温度は、好ましくは８０℃以上、より好ましくは１００℃以上であり、好ましくは１４０℃以下、より好ましくは１２０℃以下である。 The manufacturing method of the above connection structure is not particularly limited. As an example of a method for manufacturing a connection structure, the conductive material is arranged between a first connection target member and a second connection target member, and after obtaining a laminate, the laminate is heated and pressurized. The method and the like can be mentioned. The pressure at the time of pressurization is preferably 40 MPa or more, more preferably 60 MPa or more, preferably 90 MPa or less, and more preferably 70 MPa or less. The temperature at the time of heating is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 140 ° C. or lower, and more preferably 120 ° C. or lower.
　上記第１の接続対象部材及び第２の接続対象部材は、特に限定されない。上記第１の接続対象部材及び第２の接続対象部材としては、具体的には、半導体チップ、半導体パッケージ、ＬＥＤチップ、ＬＥＤパッケージ、コンデンサ及びダイオード等の電子部品、並びに樹脂フィルム、プリント基板、フレキシブルプリント基板、フレキシブルフラットケーブル、リジッドフレキシブル基板、ガラスエポキシ基板及びガラス基板等の回路基板等の電子部品等が挙げられる。上記第１の接続対象部材及び第２の接続対象部材は、電子部品であることが好ましい。 The first connection target member and the second connection target member are not particularly limited. Specific examples of the first connection target member and the second connection target member include electronic components such as semiconductor chips, semiconductor packages, LED chips, LED packages, capacitors and diodes, resin films, printed circuit boards, and flexible devices. Examples thereof include electronic components such as printed circuit boards, flexible flat cables, rigid flexible boards, glass epoxy boards, and circuit boards such as glass boards. The first connection target member and the second connection target member are preferably electronic components.
　上記導電材料は、電子部品を接続するための導電材料であることが好ましい。上記導電ペーストはペースト状の導電材料であり、ペースト状の状態で接続対象部材上に塗工されることが好ましい。 The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in the paste-like state.
　上記導電性粒子、上記導電材料及び上記接続材料は、タッチパネルにも好適に用いられる。従って、上記接続対象部材は、フレキシブル基板であるか、又は樹脂フィルムの表面上に電極が配置された接続対象部材であることも好ましい。上記接続対象部材は、フレキシブル基板であることが好ましく、樹脂フィルムの表面上に電極が配置された接続対象部材であることが好ましい。上記フレキシブル基板がフレキシブルプリント基板等である場合に、フレキシブル基板は一般に電極を表面に有する。 The conductive particles, the conductive material, and the connecting material are preferably used for a touch panel. Therefore, it is also preferable that the connection target member is a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film. The connection target member is preferably a flexible substrate, and is preferably a connection target member in which electrodes are arranged on the surface of the resin film. When the flexible substrate is a flexible printed circuit board or the like, the flexible substrate generally has electrodes on its surface.
　上記接続対象部材に設けられている電極としては、金電極、ニッケル電極、錫電極、アルミニウム電極、銅電極、モリブデン電極、銀電極、ＳＵＳ電極、及びタングステン電極等の金属電極が挙げられる。上記接続対象部材がフレキシブルプリント基板である場合には、上記電極は金電極、ニッケル電極、錫電極、銀電極又は銅電極であることが好ましい。上記接続対象部材がガラス基板である場合には、上記電極はアルミニウム電極、銅電極、モリブデン電極又はタングステン電極であることが好ましい。なお、上記電極がアルミニウム電極である場合には、アルミニウムのみで形成された電極であってもよく、金属酸化物層の表面にアルミニウム層が積層された電極であってもよい。上記金属酸化物層の材料としては、３価の金属元素がドープされた酸化インジウム及び３価の金属元素がドープされた酸化亜鉛等が挙げられる。上記３価の金属元素としては、Ｓｎ、Ａｌ及びＧａ等が挙げられる。 Examples of the electrodes provided on the connection target member include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes, SUS electrodes, and tungsten electrodes. When the connection target member is a flexible printed substrate, the electrodes are preferably gold electrodes, nickel electrodes, tin electrodes, silver electrodes or copper electrodes. When the member to be connected is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. When the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al and Ga.
　また、上記樹脂粒子は、液晶表示素子用スペーサとして好適に用いることができる。上記第１の接続対象部材は、第１の液晶表示素子用部材であってもよい。上記第２の接続対象部材は、第２の液晶表示素子用部材であってもよい。上記接続部は、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材とが対向した状態で、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材との外周をシールしているシール部であってもよい。 Further, the resin particles can be suitably used as a spacer for a liquid crystal display element. The first connection target member may be a first liquid crystal display element member. The second connection target member may be a second liquid crystal display element member. In the connecting portion, the first liquid crystal display element member and the second liquid crystal display element member are in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other. It may be a sealing portion that seals the outer periphery of and.
　上記樹脂粒子は、液晶表示素子用周辺シール剤に用いることもできる。液晶表示素子は、第１の液晶表示素子用部材と、第２の液晶表示素子用部材とを備える。液晶表示素子は、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材とが対向した状態で、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材との外周をシールしているシール部と、上記シール部の内側で、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材との間に配置されている液晶とをさらに備える。この液晶表示素子では、液晶滴下工法が適用され、かつ上記シール部が、液晶滴下工法用シール剤を熱硬化させることにより形成されている。 The resin particles can also be used as a peripheral sealant for a liquid crystal display element. The liquid crystal display element includes a first liquid crystal display element member and a second liquid crystal display element member. In the liquid crystal display element, the first liquid crystal display element member and the second liquid crystal display element member are in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other. A seal portion that seals the outer periphery of the liquid crystal, and a liquid crystal that is arranged inside the seal portion between the first liquid crystal display element member and the second liquid crystal display element member. Be prepared. In this liquid crystal display element, the liquid crystal dropping method is applied, and the sealing portion is formed by thermosetting the sealing agent for the liquid crystal dropping method.
　上記液晶表示素子において１ｍｍ２あたりの液晶表示素子用スペーサの配置密度は、好ましくは１０個／ｍｍ２以上であり、好ましくは１０００個／ｍｍ２以下である。上記配置密度が１０個／ｍｍ２以上であると、セルギャップがより一層均一になる。上記配置密度が１０００個／ｍｍ２以下であると、液晶表示素子のコントラストがより一層良好になる。 In the liquid crystal display element, the arrangement density of the spacers for the liquid crystal display element per 1 mm 2 is preferably 10 pieces / mm 2 or more, and preferably 1000 pieces / mm 2 or less. When the arrangement density is 10 pieces / mm 2 or more, the cell gap becomes even more uniform. When the arrangement density is 1000 pieces / mm 2 or less, the contrast of the liquid crystal display element becomes even better.
　（電子部品装置）
　上述した樹脂粒子又は導電性粒子は、第１のセラミック部材と第２のセラミック部材との外周部において、第１のセラミック部材と第２のセラミック部材との間に配置され、ギャップ制御材及び導電接続材として用いることもできる。 (Electronic component equipment)
The resin particles or conductive particles described above are arranged between the first ceramic member and the second ceramic member at the outer peripheral portion of the first ceramic member and the second ceramic member, and are a gap control material and a conductive material. It can also be used as a connecting material.
　図６は、本発明に係る樹脂粒子を用いた電子部品装置の一例を示す断面図である。図７は、図６に示す電子部品装置における接合部部分を拡大して示す断面図である。 FIG. 6 is a cross-sectional view showing an example of an electronic component device using the resin particles according to the present invention. FIG. 7 is an enlarged cross-sectional view showing a joint portion in the electronic component device shown in FIG.
　図６，７に示す電子部品装置８１は、第１のセラミック部材８２と、第２のセラミック部材８３と、接合部８４と、電子部品８５と、リードフレーム８６とを備える。 The electronic component device 81 shown in FIGS. 6 and 7 includes a first ceramic member 82, a second ceramic member 83, a joint portion 84, an electronic component 85, and a lead frame 86.
　第１，第２のセラミック部材８２，８３はそれぞれ、セラミック材料により形成されている。第１，第２のセラミック部材８２，８３はそれぞれ、例えば、筐体である。第１のセラミック部材８２は、例えば、基板である。第２のセラミック部材８３は、例えば蓋である。第１のセラミック部材８２は、外周部に、第２のセラミック部材８３側（上側）に突出した凸部を有する。第１のセラミック部材８２は、第２のセラミック部材８３側（上側）に、電子部品８５を収納するための内部空間Ｒを形成する凹部を有する。なお、第１のセラミック部材８２は、凸部を有していなくてもよい。第２のセラミック部材８３は、外周部に、第１のセラミック部材８２側（下側）に突出した凸部を有する。第２のセラミック部材８３は、第１のセラミック部材８２側（下側）に、電子部品８５を収納するための内部空間Ｒを形成する凹部を有する。なお、第２のセラミック部材８３は、凸部を有していなくてもよい。第１のセラミック部材８２と第２のセラミック部材８３とによって、内部空間Ｒが形成されている。 The first and second ceramic members 82 and 83 are each made of a ceramic material. The first and second ceramic members 82 and 83 are, for example, housings, respectively. The first ceramic member 82 is, for example, a substrate. The second ceramic member 83 is, for example, a lid. The first ceramic member 82 has a convex portion protruding toward the second ceramic member 83 side (upper side) on the outer peripheral portion. The first ceramic member 82 has a recess on the second ceramic member 83 side (upper side) that forms an internal space R for accommodating the electronic component 85. The first ceramic member 82 does not have to have a convex portion. The second ceramic member 83 has a convex portion protruding toward the first ceramic member 82 side (lower side) on the outer peripheral portion. The second ceramic member 83 has a recess on the first ceramic member 82 side (lower side) that forms an internal space R for accommodating the electronic component 85. The second ceramic member 83 does not have to have a convex portion. The internal space R is formed by the first ceramic member 82 and the second ceramic member 83.
　接合部８４は、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部とを接合している。具体的には、接合部８４は、第１のセラミック部材８２の外周部の凸部と、第２のセラミック部材８３の外周部の凸部とを接合している。 The joint portion 84 joins the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83. Specifically, the joint portion 84 joins the convex portion of the outer peripheral portion of the first ceramic member 82 and the convex portion of the outer peripheral portion of the second ceramic member 83.
　接合部８４により接合された第１，第２のセラミック部材８２，８３によってパッケージが形成されている。パッケージによって、内部空間Ｒが形成されている。接合部８４は、内部空間Ｒを液密的及び気密的に封止している。接合部８４は、封止部である。 The package is formed by the first and second ceramic members 82 and 83 joined by the joint portion 84. The internal space R is formed by the package. The joint portion 84 seals the internal space R in a liquid-tight and airtight manner. The joint portion 84 is a sealing portion.
　電子部品８５は、上記パッケージの内部空間Ｒ内に配置されている。具体的には、第１のセラミック部材８２上に、電子部品８５が配置されている。本実施形態では、２つの電子部品８５が用いられている。 The electronic component 85 is arranged in the internal space R of the above package. Specifically, the electronic component 85 is arranged on the first ceramic member 82. In this embodiment, two electronic components 85 are used.
　接合部８４は、複数の樹脂粒子１とガラス８４Ｂとを含む。接合部８４は、ガラス粒子とは異なる複数の樹脂粒子１とガラス８４Ｂとを含む接合材料を用いて形成されている。この接合材料は、セラミックパッケージ用接合材料である。上記接合材料は、上記樹脂粒子の代わりに、上述した導電性粒子を含んでいてもよい。 The joint portion 84 includes a plurality of resin particles 1 and glass 84B. The bonding portion 84 is formed by using a bonding material containing a plurality of resin particles 1 different from the glass particles and the glass 84B. This bonding material is a bonding material for ceramic packages. The bonding material may contain the above-mentioned conductive particles instead of the above-mentioned resin particles.
　接合材料は、溶剤を含んでいてもよく、樹脂を含んでいてもよい。接合部８４では、ガラス粒子等のガラス８４Ｂが溶融及び結合した後に固化している。 The bonding material may contain a solvent or a resin. At the joint portion 84, glass 84B such as glass particles is melted and bonded and then solidified.
　電子部品としては、センサ素子、ＭＥＭＳ及びベアチップ等が挙げられる。上記センサ素子としては、圧力センサ素子、加速度センサ素子、ＣＭＯＳセンサ素子、ＣＣＤセンサ素子及び上記各種センサ素子の筐体等が挙げられる。 Examples of electronic components include sensor elements, MEMS, bare chips, and the like. Examples of the sensor element include a pressure sensor element, an acceleration sensor element, a CMOS sensor element, a CCD sensor element, and a housing of the various sensor elements.
　リードフレーム８６は、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部との間に配置されている。リードフレーム８６は、パッケージの内部空間Ｒ側と外部空間側とに延びている。電子部品８５の端子とリードフレーム８６とがワイヤーを介して、電気的に接続されている。 The lead frame 86 is arranged between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83. The lead frame 86 extends to the internal space R side and the external space side of the package. The terminal of the electronic component 85 and the lead frame 86 are electrically connected via a wire.
　接合部８４は、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部とを部分的に直接に接合しており、部分的に間接に接合している。具体的には、接合部８４は、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部との間のリードフレーム８６がある部分において、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部とをリードフレーム８６を介して間接に接合している。第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部との間のリードフレーム８６がある部分において、第１のセラミック部材８２がリードフレーム８６と接しており、リードフレーム８６が第１のセラミック部材８２と接合部８４とに接している。さらに、接合部８４がリードフレーム８６と第２のセラミック部材８３とに接しており、第２のセラミック部材８３が接合部８４と接している。接合部８４は、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部との間のリードフレーム８６がない部分において、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部とを直接に接合している。第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部との間のリードフレーム８６がない部分において、接合部８４が、第１のセラミック部材８２と第２のセラミック部材８３とに接している。 The joint portion 84 partially directly joins the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83, and partially indirectly joins them. Specifically, the joint portion 84 is the outer peripheral portion of the first ceramic member 82 at the portion where the lead frame 86 is located between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83. And the outer peripheral portion of the second ceramic member 83 are indirectly joined via the lead frame 86. In the portion where the lead frame 86 is located between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83, the first ceramic member 82 is in contact with the lead frame 86, and the lead frame 86 is in contact with the lead frame 86. It is in contact with the first ceramic member 82 and the joint portion 84. Further, the joint portion 84 is in contact with the lead frame 86 and the second ceramic member 83, and the second ceramic member 83 is in contact with the joint portion 84. The joint portion 84 is a portion between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83 where there is no lead frame 86, and the outer peripheral portion of the first ceramic member 82 and the second ceramic It is directly joined to the outer peripheral portion of the member 83. In the portion where there is no lead frame 86 between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83, the joint portion 84 is formed with the first ceramic member 82 and the second ceramic member 83. Is in contact with.
　第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部との間のリードフレーム８６がある部分において、第１のセラミック部材８２の外周部と第２のセラミック部材８３の外周部との隙間の距離は、接合部８４に含まれる複数の樹脂粒子１により制御されている。 In the portion where the lead frame 86 is located between the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83, the outer peripheral portion of the first ceramic member 82 and the outer peripheral portion of the second ceramic member 83. The distance between the two and the ceramic particles 1 is controlled by a plurality of resin particles 1 contained in the joint portion 84.
　接合部は、第１のセラミック部材の外周部と第２のセラミック部材の外周部とを直接又は間接に接合していればよい。なお、リードフレーム以外の電気的接続方法を採用してもよい。 The joint portion may be a direct or indirect joint between the outer peripheral portion of the first ceramic member and the outer peripheral portion of the second ceramic member. An electrical connection method other than the lead frame may be adopted.
　電子部品装置８１のように、電子部品装置は、例えば、セラミック材料により形成されている第１のセラミック部材と、セラミック材料により形成されている第２のセラミック部材と、接合部と、電子部品とを備えていてもよい。上記電子部品装置では、上記接合部が、上記第１のセラミック部材の外周部と上記第２のセラミック部材の外周部とを直接又は間接に接合していてもよい。上記電子部品装置では、上記接合部により接合された上記第１，第２のセラミック部材によってパッケージが形成されていてもよい。上記電子部品装置では、上記電子部品が、上記パッケージの内部空間内に配置されており、上記接合部が、複数の樹脂粒子とガラスとを含んでいてもよい。 Like the electronic component device 81, the electronic component device includes, for example, a first ceramic member formed of a ceramic material, a second ceramic member formed of a ceramic material, a joint portion, and an electronic component. May be provided. In the electronic component device, the joint portion may directly or indirectly join the outer peripheral portion of the first ceramic member and the outer peripheral portion of the second ceramic member. In the electronic component device, the package may be formed by the first and second ceramic members joined by the joining portion. In the electronic component device, the electronic component is arranged in the internal space of the package, and the joint may include a plurality of resin particles and glass.
　また、電子部品装置８１で用いた接合材料のように、上記セラミックパッケージ用接合材料は、上記電子部品装置において、上記接合部を形成するために用いられ、樹脂粒子と、ガラスとを含む。なお、樹脂粒子のみを含み、ガラスを含まない電気的接続方法を採用してもよい。また、上記接合部は、上記樹脂粒子の代わりに、上述した導電性粒子を含んでいてもよい。 Further, like the bonding material used in the electronic component device 81, the ceramic package bonding material is used in the electronic component device to form the bonding portion, and includes resin particles and glass. An electrical connection method containing only resin particles and not glass may be adopted. Further, the joint portion may contain the above-mentioned conductive particles instead of the above-mentioned resin particles.
　以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
　（実施例１）
　（１）樹脂粒子の作製
　温度計、撹拌機、冷却管を備えた反応容器に、ビスフェノールＡ型エポキシ樹脂（ＤＩＣ社製「ＥＸＡ－８５０－ＣＲＰ」）１５重量部と、分散安定剤としてポリビニルピロリドン７．５重量部と、エタノール２５０重量部とを投入し、６８℃で１時間撹拌することで均一に溶解させた。次に、４，４’－ジアミノジフェニルメタン４．２５重量部と、エタノール３５重量部とを投入し、均一に溶解させた後、反応容器内に添加し、６８℃及び２０時間の条件で反応させ、反応生成物を得た。得られた反応生成物を洗浄し、乾燥させて、樹脂粒子を得た。 (Example 1)
(1) Preparation of resin particles In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 15 parts by weight of bisphenol A type epoxy resin (“EXA-850-CRP” manufactured by DIC) and polyvinylpyrrolidone as a dispersion stabilizer. 7.5 parts by weight and 250 parts by weight of ethanol were added, and the mixture was uniformly dissolved by stirring at 68 ° C. for 1 hour. Next, 4.25 parts by weight of 4,4'-diaminodiphenylmethane and 35 parts by weight of ethanol were added and dissolved uniformly, then added into a reaction vessel and reacted at 68 ° C. for 20 hours. , The reaction product was obtained. The obtained reaction product was washed and dried to obtain resin particles.
　（２）導電性粒子の作製
　パラジウム触媒液を５重量％含むアルカリ溶液１００重量部に、得られた樹脂粒子１０重量部を、超音波分散器を用いて分散させた後、溶液をろ過することにより、樹脂粒子を取り出した。次いで、樹脂粒子をジメチルアミンボラン１重量％溶液１００重量部に添加し、樹脂粒子の表面を活性化させた。表面が活性化された樹脂粒子を十分に水洗した後、蒸留水５００重量部に加え、分散させることにより、分散液を得た。 (2) Preparation of Conductive Particles 10 parts by weight of the obtained resin particles are dispersed in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then the solution is filtered. The resin particles were taken out. Next, the resin particles were added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the resin particles. The surface-activated resin particles were thoroughly washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a dispersion liquid.
　また、硫酸ニッケル０．３５ｍｏｌ／Ｌ、ジメチルアミンボラン１．３８ｍｏｌ／Ｌ及びクエン酸ナトリウム０．５ｍｏｌ／Ｌを含むニッケルめっき液（ｐＨ８．５）を用意した。 Further, a nickel plating solution (pH 8.5) containing nickel sulfate 0.35 mol / L, dimethylamine borane 1.38 mol / L and sodium citrate 0.5 mol / L was prepared.
　得られた分散液を６０℃にて攪拌しながら、上記ニッケルめっき液を分散液に徐々に滴下し、無電解ニッケルめっきを行った。その後、分散液をろ過することにより、粒子を取り出し、水洗し、乾燥することにより、樹脂粒子の表面にニッケル－ボロン導電層が形成され、導電部を表面に有する導電性粒子を得た。 While stirring the obtained dispersion at 60 ° C., the nickel plating solution was gradually added dropwise to the dispersion to perform electroless nickel plating. Then, the dispersion liquid was filtered to take out the particles, washed with water, and dried to form a nickel-boron conductive layer on the surface of the resin particles to obtain conductive particles having a conductive portion on the surface.
　（３）導電材料（異方性導電ペースト）の作製
　得られた導電性粒子７重量部と、ビスフェノールＡ型フェノキシ樹脂２５重量部と、フルオレン型エポキシ樹脂４重量部と、フェノールノボラック型エポキシ樹脂３０重量部と、ＳＩ－６０Ｌ（三新化学工業社製）とを配合して、３分間脱泡及び攪拌することで、導電材料（異方性導電ペースト）を得た。 (3) Preparation of Conductive Material (Anisically Conductive Paste) 7 parts by weight of the obtained conductive particles, 25 parts by weight of bisphenol A type phenoxy resin, 4 parts by weight of fluorene type epoxy resin, and 30 parts by weight of phenol novolac type epoxy resin. A conductive material (anisotropic conductive paste) was obtained by blending a weight portion and SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.), defoaming and stirring for 3 minutes.
　（４）接続構造体の作製
　Ｌ／Ｓが１０μｍ／１０μｍであるＩＺＯ電極パターン（第１の電極、電極表面の金属のビッカース硬度１００Ｈｖ）が上面に形成された透明ガラス基板（第１の接続対象部材）を用意した。また、Ｌ／Ｓが１０μｍ／１０μｍであるＡｕ電極パターン（第２の電極、電極表面の金属のビッカース硬度５０Ｈｖ）が下面に形成された半導体チップ（第２の接続対象部材）を用意した。上記透明ガラス基板上に、得られた異方性導電ペーストを厚さ３０μｍとなるように塗工し、異方性導電ペースト層を形成した。次に、異方性導電ペースト層上に上記半導体チップを、電極同士が対向するように積層した。その後、異方性導電ペースト層の温度が１００℃となるようにヘッドの温度を調整しながら、半導体チップの上面に加圧加熱ヘッドを載せ、５５ＭＰａの圧力をかけて異方性導電ペースト層を１００℃で硬化させ、接続構造体を得た。 (4) Preparation of Connection Structure A transparent glass substrate (first connection target) in which an IZO electrode pattern (first electrode, Vickers hardness of metal on the electrode surface 100 Hv) having an L / S of 10 μm / 10 μm is formed on the upper surface. Members) were prepared. Further, a semiconductor chip (second connection target member) having an Au electrode pattern (second electrode, Vickers hardness of metal on the electrode surface 50 Hv) having an L / S of 10 μm / 10 μm formed on the lower surface was prepared. The obtained anisotropic conductive paste was coated on the transparent glass substrate so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. Next, the semiconductor chips were laminated on the anisotropic conductive paste layer so that the electrodes face each other. After that, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100 ° C., the pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 55 MPa is applied to form the anisotropic conductive paste layer. It was cured at 100 ° C. to obtain a connection structure.
　（実施例２）
　樹脂粒子の作製の際に、ビスフェノールＡ型エポキシ樹脂の代わりにグリシジルアミン型エポキシ樹脂（三菱ガス化学社製「ＴＥＴＲＡＤ－Ｘ」）を用い、エタノールの代わりにイソプロピルアルコールを用いた。また、樹脂粒子の作製の際の４，４’－ジアミノジフェニルメタンの配合量を７．５３重量部に変更した。上記の変更以外は、実施例１と同様にして、樹脂粒子、導電性粒子、導電材料、及び接続構造体を得た。 (Example 2)
In the production of the resin particles, a glycidylamine type epoxy resin (“TETRAD-X” manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of the bisphenol A type epoxy resin, and isopropyl alcohol was used instead of ethanol. Moreover, the compounding amount of 4,4'-diaminodiphenylmethane at the time of producing the resin particles was changed to 7.53 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
　（実施例３）
　樹脂粒子の作製の際に、ビスフェノールＡ型エポキシ樹脂の代わりにトリアジン型エポキシ樹脂（日産化学社製「ＴＥＰＩＣ－ＰＡＳ」）を用いた。また、樹脂粒子の作製の際に、４，４’－ジアミノジフェニルメタン４．２５重量部の代わりにエチレンジアミン１．６３重量部を用いた。上記の変更以外は、実施例１と同様にして、樹脂粒子、導電性粒子、導電材料、及び接続構造体を得た。 (Example 3)
When producing the resin particles, a triazine type epoxy resin (“TEPIC-PAS” manufactured by Nissan Chemical Industries, Ltd.) was used instead of the bisphenol A type epoxy resin. Further, when producing the resin particles, 1.63 parts by weight of ethylenediamine was used instead of 4.25 parts by weight of 4,4′-diaminodiphenylmethane. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
　（実施例４）
　樹脂粒子の作製の際に、ビスフェノールＡ型エポキシ樹脂の代わりにグリシジルアミン型エポキシ樹脂（三菱ケミカル社製「ＪＥＲ－６３０」）を用いた。また、樹脂粒子の作製の際の４，４’－ジアミノジフェニルメタンの配合量を７．６３重量部に変更した。上記の変更以外は、実施例１と同様にして、樹脂粒子、導電性粒子、導電材料、及び接続構造体を得た。 (Example 4)
When producing the resin particles, a glycidylamine type epoxy resin (“JER-630” manufactured by Mitsubishi Chemical Corporation) was used instead of the bisphenol A type epoxy resin. In addition, the amount of 4,4'-diaminodiphenylmethane blended in the preparation of the resin particles was changed to 7.63 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
　（実施例５）
　樹脂粒子の作製の際に、ビスフェノールＡ型エポキシ樹脂の代わりに脂環式グリシジルアミン型エポキシ樹脂（三菱ガス化学社製「ＴＥＴＲＡＤ－Ｃ」）を用い、エタノールの代わりにイソプロピルアルコールを用いた。また、樹脂粒子の作製の際の４，４’－ジアミノジフェニルメタンの配合量を７．４４重量部に変更した。上記の変更以外は、実施例１と同様にして、樹脂粒子、導電性粒子、導電材料、及び接続構造体を得た。 (Example 5)
When producing the resin particles, an alicyclic glycidylamine type epoxy resin (“TETRAD-C” manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of the bisphenol A type epoxy resin, and isopropyl alcohol was used instead of ethanol. In addition, the blending amount of 4,4'-diaminodiphenylmethane at the time of producing the resin particles was changed to 7.44 parts by weight. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
　（実施例６）
　実施例１と同様にして、樹脂粒子を得た。導電性粒子の作製の際に、分散液中に、ニッケル粒子スラリー（平均粒子径１００ｎｍ）１ｇを３分間かけて添加し、芯物質が付着した樹脂粒子を含む懸濁液を得た。上記分散液の代わりに上記懸濁液を用いたこと以外は、実施例１と同様にして、導電性粒子、導電材料、及び接続構造体を得た。 (Example 6)
Resin particles were obtained in the same manner as in Example 1. At the time of producing the conductive particles, 1 g of nickel particle slurry (average particle diameter 100 nm) was added to the dispersion liquid over 3 minutes to obtain a suspension containing the resin particles to which the core substance was attached. Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the suspension was used instead of the dispersion.
　（実施例７）
　（１）絶縁性粒子の作製
　４つ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブを取り付けた１０００ｍＬセパラブルフラスコに、下記のモノマー組成物を入れた後、下記モノマー組成物の固形分が１０重量％となるように蒸留水を入れ、２００ｒｐｍで攪拌し、窒素雰囲気下６０℃で２４時間重合を行った。上記モノマー組成物は、メタクリル酸メチル３６０ｍｍｏｌ、メタクリル酸グリシジル４５ｍｍｏｌ、パラスチリルジエチルホスフィン２０ｍｍｏｌ、ジメタクリル酸エチレングリコール１３ｍｍｏｌ、ポリビニルピロリドン０．５ｍｍｏｌ、及び２，２’－アゾビス｛２－［Ｎ－（２－カルボキシエチル）アミジノ］プロパン｝１ｍｍｏｌを含む。反応終了後、凍結乾燥して、パラスチリルジエチルホスフィンに由来するリン原子を表面に有する絶縁性粒子（粒子径３６０ｎｍ）を得た。 (Example 7)
(1) Preparation of Insulating Particles After putting the following monomer composition in a 1000 mL separable flask equipped with a four-mouth separable cover, a stirring blade, a three-way cock, a cooling tube and a temperature probe, the following monomer composition Distilled water was added so that the solid content was 10% by weight, the mixture was stirred at 200 rpm, and polymerization was carried out at 60 ° C. for 24 hours under a nitrogen atmosphere. The monomer composition comprises 360 mmol of methyl methacrylate, 45 mmol of glycidyl methacrylate, 20 mmol of parastyryldiethylphosphine, 13 mmol of ethylene glycol dimethacrylate, 0.5 mmol of polyvinylpyrrolidone, and 2,2'-azobis {2- [N- (2). -Carboxyethyl) amidino] propane} 1 mmol. After completion of the reaction, freeze-drying was performed to obtain insulating particles (particle diameter 360 nm) having a phosphorus atom derived from parastilyl diethylphosphine on the surface.
　（２）絶縁性粒子付き導電性粒子の作製
　実施例６で得られた導電性粒子を用意した。上記で得られた絶縁性粒子を超音波照射下で蒸留水に分散させ、絶縁性粒子の１０重量％水分散液を得た。用意した導電性粒子１０ｇを蒸留水５００ｍＬに分散させ、絶縁性粒子の１０重量％水分散液１ｇを添加し、室温で８時間攪拌した。３μｍのメッシュフィルターでろ過した後、さらにメタノールで洗浄、乾燥し、絶縁性粒子付き導電性粒子を得た。上記導電性粒子の代わりに上記絶縁性粒子付き導電性粒子を用いたこと以外は、実施例１と同様にして、導電材料、及び接続構造体を得た。 (2) Preparation of Conductive Particles with Insulating Particles The conductive particles obtained in Example 6 were prepared. The insulating particles obtained above were dispersed in distilled water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of the insulating particles. 10 g of the prepared conductive particles were dispersed in 500 mL of distilled water, 1 g of a 10 wt% aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 8 hours. After filtering with a 3 μm mesh filter, the mixture was further washed with methanol and dried to obtain conductive particles with insulating particles. A conductive material and a connecting structure were obtained in the same manner as in Example 1 except that the conductive particles with insulating particles were used instead of the conductive particles.
　（実施例８）
　種粒子として平均粒子径０．９３μｍのポリスチレン粒子を用意した。上記ポリスチレン粒子３．９重量部と、イオン交換水５００重量部と、ポリビニルアルコールの５重量％水溶液１２０重量部とを混合し、混合液を調製した。上記混合液を超音波により分散させた後、セパラブルフラスコに入れて、均一に撹拌した。 (Example 8)
Polystyrene particles having an average particle diameter of 0.93 μm were prepared as seed particles. A mixed solution was prepared by mixing 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol. After the above mixed solution was dispersed by ultrasonic waves, it was placed in a separable flask and stirred uniformly.
　次に、２，２’－アゾビス（イソ酪酸メチル）（和光純薬工業社製「Ｖ－６０１」）２重量部と、過酸化ベンゾイル（日油社製「ナイパーＢＷ」）２重量部とを混合した。さらに、イソボニルジアクリレート１２０重量部と、スチレン３０重量部と、ラウリル硫酸トリエタノールアミン９重量部と、エタノール３０重量部と、イオン交換水１１００重量部とを添加し、乳化液を調製した。 Next, 2 parts by weight of 2,2'-azobis (methyl isobutyrate) ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.) and 2 parts by weight of benzoyl peroxide ("Niper BW" manufactured by NOF Corporation) were added. Mixed. Further, 120 parts by weight of isobonyl diacrylate, 30 parts by weight of styrene, 9 parts by weight of triethanolamine lauryl sulfate, 30 parts by weight of ethanol, and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.
　セパラブルフラスコ中の上記混合液に、上記乳化液を数回に分けて添加し、１２時間撹拌し、種粒子にモノマーを吸収させて、モノマーが膨潤した種粒子を含む懸濁液を得た。 The emulsion was added to the mixture in the separable flask in several portions and stirred for 12 hours to allow the seed particles to absorb the monomer to obtain a suspension containing the seed particles in which the monomer was swollen. ..
　その後、ポリビニルアルコールの５重量％水溶液４９０重量部を添加し、加熱を開始して８５℃で９時間反応させ、樹脂粒子を得た。 Then, 490 parts by weight of a 5 wt% aqueous solution of polyvinyl alcohol was added, heating was started, and the mixture was reacted at 85 ° C. for 9 hours to obtain resin particles.
　得られた樹脂粒子を用いたこと以外は、実施例１と同様にして、導電性粒子、導電材料、及び接続構造体を得た。 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the obtained resin particles were used.
　（実施例９）
　樹脂粒子の作製の際に、４，４’－ジアミノジフェニルメタン４．２５重量部の代わりに１，４－フェニレンジアミン２．３４重量部を用いた。上記の変更以外は、実施例１と同様にして、樹脂粒子、導電性粒子、導電材料、及び接続構造体を得た。 (Example 9)
In the preparation of the resin particles, 2.34 parts by weight of 1,4-phenylenediamine was used instead of 4.25 parts by weight of 4,4'-diaminodiphenylmethane. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
　（実施例１０）
　樹脂粒子の作製の際に、４，４’－ジアミノジフェニルメタン４．２５重量部の代わりに２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン８．９０重量部を用いた。上記の変更以外は、実施例１と同様にして、樹脂粒子、導電性粒子、導電材料、及び接続構造体を得た。 (Example 10)
In the preparation of the resin particles, 8.90 parts by weight of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was used instead of 4.25 parts by weight of 4,4'-diaminodiphenylmethane. Except for the above changes, resin particles, conductive particles, conductive materials, and a connecting structure were obtained in the same manner as in Example 1.
　（比較例１）
　種粒子として平均粒子径０．９３μｍのポリスチレン粒子を用意した。上記ポリスチレン粒子３．９重量部と、イオン交換水５００重量部と、ポリビニルアルコールの５重量％水溶液１２０重量部とを混合し、混合液を調製した。上記混合液を超音波により分散させた後、セパラブルフラスコに入れて、均一に撹拌した。 (Comparative Example 1)
Polystyrene particles having an average particle diameter of 0.93 μm were prepared as seed particles. A mixed solution was prepared by mixing 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol. After the above mixed solution was dispersed by ultrasonic waves, it was placed in a separable flask and stirred uniformly.
　次に、２，２’－アゾビス（イソ酪酸メチル）（和光純薬工業社製「Ｖ－６０１」）２重量部と、過酸化ベンゾイル（日油社製「ナイパーＢＷ」）２重量部とを混合し、さらにジビニルベンゼン１５０重量部と、ラウリル硫酸トリエタノールアミン９重量部と、エタノール３０重量部と、イオン交換水１１００重量部とを添加し、乳化液を調製した。 Next, 2 parts by weight of 2,2'-azobis (methyl isobutyrate) ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.) and 2 parts by weight of benzoyl peroxide ("Niper BW" manufactured by Nichiyu Co., Ltd.) were added. After mixing, 150 parts by weight of divinylbenzene, 9 parts by weight of triethanolamine lauryl sulfate, 30 parts by weight of ethanol, and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.
　セパラブルフラスコ中の上記混合液に、上記乳化液を数回に分けて添加し、１２時間撹拌し、種粒子にモノマーを吸収させて、モノマーが膨潤した種粒子を含む懸濁液を得た。 The emulsion was added to the mixture in the separable flask in several portions and stirred for 12 hours to allow the seed particles to absorb the monomer to obtain a suspension containing the seed particles in which the monomer was swollen. ..
　その後、ポリビニルアルコールの５重量％水溶液４９０重量部を添加し、加熱を開始して８５℃で９時間反応させ、樹脂粒子を得た。 Then, 490 parts by weight of a 5 wt% aqueous solution of polyvinyl alcohol was added, heating was started, and the mixture was reacted at 85 ° C. for 9 hours to obtain resin particles.
　得られた樹脂粒子を用いたこと以外は、実施例１と同様にして、導電性粒子、導電材料、及び接続構造体を得た。 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the obtained resin particles were used.
　（比較例２）
　ジビニルベンゼン１５０重量部の代わりに、１，６－ヘキサンジオールジメタクリレート３０重量部とスチレン１２０重量部とを用いたこと以外は、比較例１と同様にして、導電性粒子、導電材料、及び接続構造体を得た。 (Comparative Example 2)
Conductive particles, conductive materials, and connections in the same manner as in Comparative Example 1, except that 30 parts by weight of 1,6-hexanediol dimethacrylate and 120 parts by weight of styrene were used instead of 150 parts by weight of divinylbenzene. Obtained a structure.
　（比較例３）
　樹脂粒子として、日産化学社製「オプトビーズ３５００Ｍ」を用意した。用意した樹脂粒子を用いたこと以外は、実施例１と同様にして、導電性粒子、導電材料、及び接続構造体を得た。 (Comparative Example 3)
As the resin particles, "Optobeads 3500M" manufactured by Nissan Chemical Industries, Ltd. was prepared. Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the prepared resin particles were used.
　（評価）
　（１）樹脂粒子の粒子径（数平均粒子径）
　得られた樹脂粒子について、粒度分布測定装置（ベックマンコールター社製「Ｍｕｌｔｉｓｉｚｅｒ４」）を用いて、約１０００００個の樹脂粒子の粒子径を測定し、平均値を算出した。 (Evaluation)
(1) Particle diameter of resin particles (number average particle diameter)
With respect to the obtained resin particles, the particle diameters of about 100,000 resin particles were measured using a particle size distribution measuring device (“Multisizer 4” manufactured by Beckman Coulter), and an average value was calculated.
　（２）樹脂粒子のアスペクト比
　得られた樹脂粒子を電子顕微鏡にて観察し、アスペクト比を求めた。なお、上記アスペクト比として、任意の樹脂粒子５０個のアスペクト比の平均値を採用した。 (2) Aspect ratio of resin particles The obtained resin particles were observed with an electron microscope to determine the aspect ratio. As the aspect ratio, the average value of the aspect ratios of 50 arbitrary resin particles was adopted.
　（３）圧縮解放後の樹脂粒子の形状
　材質がガラスである第１の板及び第２の板を用意した。第１の板及び第２の板はそれぞれ、平面を有する。第１の板の表面の末端に、ギャップ材として、樹脂粒子の粒子径の７０％の厚みを有するポリイミドフィルムを貼り付けた。第１の板及び第２の板の表面温度が２００℃となるように加熱した後、加熱された第１の板の表面に、得られた樹脂粒子を配置した。樹脂粒子を配置してから３分以上５分以内に、万力熱プレス機デジタル（アズワン社製「ＭＮＰ２－００２Ｄ」）を用いて、第１の板と第２の板との間の距離が、樹脂粒子の粒子径（数平均粒子径）の７０％となる位置まで、第１の板又は第２の板を移動させた。すなわち、樹脂粒子を粒子径（数平均粒子径）に対して３０％圧縮した。圧縮条件は、圧縮速度２０００ｍＮ／秒及び荷重２００００ｍＮの条件とした。樹脂粒子を３０％圧縮した状態で、荷重２００００ｍＮで２００℃にて１０分間保持した後、圧縮を解放した。圧縮解放後の樹脂粒子を無風条件下で２５℃にて１時間放置した後、該樹脂粒子を電子顕微鏡で撮影した。 (3) Shape of Resin Particles After Compression Release A first plate and a second plate whose material is glass were prepared. The first plate and the second plate each have a flat surface. A polyimide film having a thickness of 70% of the particle diameter of the resin particles was attached to the end of the surface of the first plate as a gap material. After heating so that the surface temperature of the first plate and the second plate became 200 ° C., the obtained resin particles were arranged on the surface of the heated first plate. Within 3 to 5 minutes after arranging the resin particles, the distance between the first plate and the second plate was reduced using a vise heat press digital (“MNP2-002D” manufactured by AS ONE Corporation). , The first plate or the second plate was moved to a position where it became 70% of the particle diameter (number average particle diameter) of the resin particles. That is, the resin particles were compressed by 30% with respect to the particle size (number average particle size). The compression conditions were a compression speed of 2000 mN / sec and a load of 20000 mN. The resin particles were held at 200 ° C. for 10 minutes under a load of 20000 mN in a state of being compressed by 30%, and then the compression was released. The resin particles after compression release were left at 25 ° C. for 1 hour under windless conditions, and then the resin particles were photographed with an electron microscope.
　得られた顕微鏡写真から、樹脂粒子５０個を選択し、圧縮方向と直交する方向から観察される圧縮解放後の樹脂粒子のアスペクト比及びアスペクト比の変動係数（ＣＶ値）を求めた。 From the obtained micrographs, 50 resin particles were selected, and the aspect ratio of the resin particles after compression and release observed from the direction orthogonal to the compression direction and the coefficient of variation (CV value) of the aspect ratio were obtained.
　（４）熱分解温度
　示差熱熱重量同時測定装置（日立ハイテクサイエンス社製「ＴＧ／ＤＴＡ：ＳＴＡ７２００」）を用いて、得られた樹脂粒子の熱分解温度を測定した。なお熱分解温度は、上記樹脂粒子１０ｍｇを空気中で５℃／ｍｉｎで昇温し、測定結果における重量が１０％減少したときの温度である。 (4) Pyrolysis temperature The thermal decomposition temperature of the obtained resin particles was measured using a differential thermal thermal weight simultaneous measuring device (“TG / DTA: STA7200” manufactured by Hitachi High-Tech Science Co., Ltd.). The thermal decomposition temperature is the temperature at which 10 mg of the resin particles are heated in air at 5 ° C./min and the weight in the measurement result is reduced by 10%.
　（５）１０％Ｋ値及び３０％Ｋ値
　得られた樹脂粒子の１０％圧縮したときの圧縮弾性率（１０％Ｋ値）及び３０％圧縮したときの圧縮弾性率（３０％Ｋ値）、並びに、得られた導電性粒子の１０％圧縮したときの圧縮弾性率（１０％Ｋ値）及び３０％圧縮したときの圧縮弾性率（３０％Ｋ値）を上述した方法により測定した。なお、微小圧縮試験機として、フィッシャー社製「フィッシャースコープＨ－１００」）を用いた。 (5) 10% K value and 30% K value The compressive elastic modulus (10% K value) when the obtained resin particles are compressed by 10% and the compressive elastic modulus (30% K value) when compressed by 30%. In addition, the compressive elastic modulus (10% K value) when the obtained conductive particles were compressed by 10% and the compressive elastic modulus (30% K value) when compressed by 30% were measured by the above-mentioned methods. As the microcompression tester, a Fisher Scope H-100) manufactured by Fisher Co., Ltd. was used.
　（６）導電部の厚み
　得られた導電性粒子を含有量が３０重量％となるように、Ｋｕｌｚｅｒ社製「テクノビット４０００」に添加し、分散させて、検査用埋め込み樹脂体を作製した。その検査用埋め込み樹脂体中に分散した導電性粒子の中心付近を通るようにイオンミリング装置（日立ハイテクノロジーズ社製「ＩＭ４０００」）を用いて、導電性粒子の断面を切り出した。 (6) Thickness of Conductive Part The obtained conductive particles were added to "Technobit 4000" manufactured by Kulzer and dispersed so as to have a content of 30% by weight to prepare an embedded resin body for inspection. A cross section of the conductive particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the embedded resin body for inspection.
　そして、電界放射型透過電子顕微鏡（ＦＥ－ＴＥＭ）（日本電子社製「ＪＥＭ－ＡＲＭ２００Ｆ」）を用いて、画像倍率５万倍に設定し、５０個の導電性粒子を無作為に選択し、それぞれの導電性粒子の導電部を観察した。各導電性粒子における導電部の厚みを計測し、それを算術平均して導電部の厚みとした。 Then, using a field emission transmission electron microscope (FE-TEM) (“JEM-ARM200F” manufactured by JEOL Ltd.), the image magnification was set to 50,000 times, and 50 conductive particles were randomly selected. The conductive part of each conductive particle was observed. The thickness of the conductive portion of each conductive particle was measured and arithmetically averaged to obtain the thickness of the conductive portion.
　（７）樹脂粒子と導電部との密着性
　得られた接続構造体について、接続部中の導電性粒子を走査型電子顕微鏡（日立ハイテクノロジーズ社製「Ｒｅｇｕｌｕｓ８２２０」）を用いて観察した。観察した導電性粒子１００個について、樹脂粒子の表面上に配置された導電部が剥離しているか否かを確認した。樹脂粒子と導電部との密着性を以下の基準で判定した。 (7) Adhesion between Resin Particles and Conductive Part With respect to the obtained connection structure, the conductive particles in the connection part were observed using a scanning electron microscope (“Regulus 8220” manufactured by Hitachi High-Technologies Corporation). With respect to the 100 conductive particles observed, it was confirmed whether or not the conductive portion arranged on the surface of the resin particles was peeled off. The adhesion between the resin particles and the conductive portion was judged according to the following criteria.
　［樹脂粒子と導電部との密着性の判定基準］
　○○○：導電部の剥離した導電性粒子が０個
　○○：導電部の剥離した導電性粒子が０個を超え１５個以下
　○：導電部の剥離した導電性粒子が１５個を超え３０個以下
　△：導電部の剥離した導電性粒子が３０個を超え５０個以下
　×：導電部の剥離した導電性粒子が５０個を超える [Criteria for determining the adhesion between resin particles and conductive parts]
○ ○ ○: 0 conductive particles with peeled conductive parts ○ ○: More than 0 conductive particles with peeled conductive parts and 15 or less ○: More than 15 conductive particles with peeled conductive parts 30 Less than or equal to Δ: More than 30 conductive particles with peeled conductive parts and less than 50 ×: More than 50 conductive particles with peeled conductive parts
　（８）導電性粒子の形状維持特性
　得られた接続構造体について、接続部中の導電性粒子を走査型電子顕微鏡（日立ハイテクノロジーズ社製「Ｒｅｇｕｌｕｓ８２２０」）を用いて観察した。観察した導電性粒子１００個について、圧縮された形状が維持されているか否かを確認した。導電性粒子の形状維持特性を以下の基準で判定した。 (8) Shape Maintaining Characteristics of Conductive Particles With respect to the obtained connection structure, the conductive particles in the connection portion were observed using a scanning electron microscope (“Regulus 8220” manufactured by Hitachi High-Technologies Corporation). It was confirmed whether or not the compressed shape of the 100 conductive particles observed was maintained. The shape-maintaining characteristics of the conductive particles were judged according to the following criteria.
　［導電性粒子の形状維持特性の判定基準］
　○○○：圧縮された形状を維持している導電性粒子の個数が９０個以上
　○○：圧縮された形状を維持している導電性粒子の個数が７０個以上９０個未満
　○：圧縮された形状を維持している導電性粒子の個数が５０個以上７０個未満
　△：圧縮された形状を維持している導電性粒子の個数が１個以上５０個未満
　×：導電性粒子が圧縮された形状を維持していないか、又は、導電性粒子が破壊されている [Criteria for determining the shape-maintaining characteristics of conductive particles]
○ ○ ○: The number of conductive particles maintaining the compressed shape is 90 or more ○ ○: The number of conductive particles maintaining the compressed shape is 70 or more and less than 90 ○: Compressed The number of conductive particles maintaining the shape is 50 or more and less than 70 Δ: The number of conductive particles maintaining the compressed shape is 1 or more and less than 50 ×: The conductive particles are compressed The shape is not maintained or the conductive particles are destroyed.
　（９）接続信頼性（上下の電極間）
　得られた接続構造体２０個の上下の電極間の接続抵抗をそれぞれ、４端子法により測定した。接続抵抗の平均値を算出した。なお、電圧＝電流×抵抗の関係から、一定の電流を流した時の電圧を測定することにより接続抵抗を求めることができる。接続信頼性を以下の基準で判定した。 (9) Connection reliability (between the upper and lower electrodes)
The connection resistance between the upper and lower electrodes of the 20 obtained connection structures was measured by the 4-terminal method, respectively. The average value of the connection resistance was calculated. From the relationship of voltage = current x resistance, the connection resistance can be obtained by measuring the voltage when a constant current is passed. The connection reliability was judged according to the following criteria.
　［接続信頼性の判定基準］
　○○○：接続抵抗の平均値が１．５Ω以下
　○○：接続抵抗の平均値が１．５Ωを超え２．０Ω以下
　○：接続抵抗の平均値が２．０Ωを超え５．０Ω以下
　△：接続抵抗の平均値が５．０Ωを超え１０Ω以下
　×：接続抵抗の平均値が１０Ωを超える [Criteria for connection reliability]
○ ○ ○: Mean value of connection resistance is 1.5Ω or less ○ ○: Mean value of connection resistance is more than 1.5Ω and 2.0Ω or less ○: Mean value of connection resistance is more than 2.0Ω and 5.0Ω or less △ : Average value of connection resistance exceeds 5.0Ω and is 10Ω or less ×: Mean value of connection resistance exceeds 10Ω
　（１０）耐衝撃性
　得られた接続構造体２０個を高さ７０ｃｍの位置から落下させて、上記（９）の評価と同様にして、接続抵抗を確認することで耐衝撃性の評価を行った。上記（９）の評価で得られた接続抵抗の平均値からの抵抗値の上昇率により耐衝撃性を以下の基準で判定した。 (10) Impact resistance The impact resistance is evaluated by dropping the obtained 20 connection structures from a height of 70 cm and checking the connection resistance in the same manner as in the evaluation of (9) above. It was. The impact resistance was determined by the following criteria based on the rate of increase of the resistance value from the average value of the connection resistances obtained in the evaluation of (9) above.
　［耐衝撃性の判定基準］
　○：接続抵抗の平均値からの抵抗値の上昇率が３０％以下
　△：接続抵抗の平均値からの抵抗値の上昇率が３０％を超え５０％以下
　×：接続抵抗の平均値からの抵抗値の上昇率が５０％を超える [Criteria for impact resistance]
◯: The rate of increase in resistance value from the average value of connection resistance is 30% or less Δ: The rate of increase in resistance value from the average value of connection resistance exceeds 30% and is 50% or less ×: Resistance from the average value of connection resistance Value increase rate exceeds 50%
　（１１）高温及び高湿条件後の接続信頼性
　得られた接続構造体１００個を、８５℃及び８５％ＲＨにて１００時間放置した。放置後の１００個の接続構造体について、上下の電極間の導通不良が生じているか否かを評価した。高温及び高湿条件後の接続信頼性を以下の基準で判定した。 (11) Connection reliability after high temperature and high humidity conditions The obtained 100 connection structures were left at 85 ° C. and 85% RH for 100 hours. For 100 connection structures after being left to stand, it was evaluated whether or not there was a conduction failure between the upper and lower electrodes. The connection reliability after high temperature and high humidity conditions was judged according to the following criteria.
　［高温及び高湿条件後の接続信頼性の判定基準］
　○○：接続構造体１００個の内、導通不良が生じている個数が１個以下である
　○：接続構造体１００個の内、導通不良が生じている個数が２個以上５個以下である
　△：接続構造体１００個の内、導通不良が生じている個数が６個以上１０個以下である
　×：接続構造体１００個の内、導通不良が生じている個数が１１個以上である [Criteria for connection reliability after high temperature and high humidity conditions]
○○: Of the 100 connection structures, the number of poor continuity is 1 or less. ○: Of the 100 connection structures, the number of poor continuity is 2 or more and 5 or less. Δ: 6 or more and 10 or less of the 100 connection structures have poor continuity. ×: 11 or more of the 100 connection structures have poor continuity.
　結果を表１，２に示す。なお、実施例１～７，９，１０では、圧縮解放後の樹脂粒子として、図８（ｂ）に類似するような電子顕微鏡写真が得られた。また、図９は、実施例８における圧縮解放後の樹脂粒子の電子顕微鏡写真である。図１０（ａ）は、比較例１における圧縮解放後の樹脂粒子の電子顕微鏡写真であり、図１０（ｂ）は、比較例２における圧縮解放後の樹脂粒子の電子顕微鏡写真であり、図１０（ｃ）は、比較例３における圧縮解放後の樹脂粒子の電子顕微鏡写真である。 The results are shown in Tables 1 and 2. In Examples 1 to 7, 9 and 10, electron micrographs similar to those in FIG. 8B were obtained as the resin particles after compression release. Further, FIG. 9 is an electron micrograph of the resin particles after compression release in Example 8. FIG. 10 (a) is an electron micrograph of the resin particles after compression and release in Comparative Example 1, and FIG. 10 (b) is an electron micrograph of the resin particles after compression and release in Comparative Example 2. FIG. (C) is an electron micrograph of the resin particles after compression and release in Comparative Example 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　１…樹脂粒子
　１ａ…第１の表面（平面部分）
　１ｂ…第２の表面（平面部分）
　２…導電部
　１１…導電性粒子
　２１…導電性粒子
　２２…導電部
　２２Ａ…第１の導電部
　２２Ｂ…第２の導電部
　３１…導電性粒子
　３１ａ…突起
　３２…導電部
　３２ａ…突起
　３３…芯物質
　３４…絶縁性物質
　４１…接続構造体
　４２…第１の接続対象部材
　４２ａ…第１の電極
　４３…第２の接続対象部材
　４３ａ…第２の電極
　４４…接続部
　８１…電子部品装置
　８２…第１のセラミック部材
　８３…第２のセラミック部材
　８４…接合部
　８４Ｂ…ガラス
　８５…電子部品
　８６…リードフレーム
　Ｐ…圧縮方向
　Ｒ…内部空間 1 ... Resin particles 1a ... First surface (flat surface)
1b ... Second surface (planar portion)
2 ... Conductive part 11 ... Conductive particles 21 ... Conductive particles 22 ... Conductive part 22A ... First conductive part 22B ... Second conductive part 31 ... Conductive particles 31a ... Protrusions 32 ... Conductive parts 32a ... Protrusions 33 ... Core Material 34 ... Insulating material 41 ... Connection structure 42 ... First connection target member 42a ... First electrode 43 ... Second connection target member 43a ... Second electrode 44 ... Connection part 81 ... Electronic component device 82 ... 1st ceramic member 83 ... 2nd ceramic member 84 ... Joint portion 84B ... Glass 85 ... Electronic component 86 ... Lead frame P ... Compression direction R ... Internal space

Claims (14)

  1. 　樹脂粒子であって、
    　前記樹脂粒子を粒子径に対して３０％圧縮した状態で２００℃にて１０分間保持した後、圧縮から解放したときに、２５℃にて、圧縮方向と直交する方向から観察される圧縮解放後の前記樹脂粒子のアスペクト比の変動係数が、１０％以下である、樹脂粒子。     Resin particles
    After the resin particles are held at 200 ° C. for 10 minutes in a state of being compressed by 30% with respect to the particle size, and then released from compression, they are observed at 25 ° C. from a direction orthogonal to the compression direction. The coefficient of variation of the aspect ratio of the resin particles is 10% or less.
  2. 　加熱により熱硬化可能である、請求項１に記載の樹脂粒子。 The resin particles according to claim 1, which can be thermoset by heating.
  3. 　熱分解温度が、２００℃以上３５０℃以下である、請求項１又は２に記載の樹脂粒子。 The resin particles according to claim 1 or 2, wherein the thermal decomposition temperature is 200 ° C. or higher and 350 ° C. or lower.
  4. 　１０％圧縮したときの圧縮弾性率が、１００Ｎ／ｍｍ２以上３５００Ｎ／ｍｍ２以下である、請求項１～３のいずれか１項に記載の樹脂粒子。 Compressive modulus upon compression 10%, 100 N / mm 2 or more 3500 N / mm 2 or less, the resin particles according to any one of claims 1 to 3.
  5. 　３０％圧縮したときの圧縮弾性率が、１００Ｎ／ｍｍ２以上３０００Ｎ／ｍｍ２以下である、請求項１～４のいずれか１項に記載の樹脂粒子。 The resin particle according to any one of claims 1 to 4, wherein the compressive elastic modulus when compressed by 30% is 100 N / mm 2 or more and 3000 N / mm 2 or less.
  6. 　前記圧縮方向と直交する方向から観察される圧縮解放後の前記樹脂粒子のアスペクト比が、１．１以上である、請求項１～５のいずれか１項に記載の樹脂粒子。 The resin particle according to any one of claims 1 to 5, wherein the aspect ratio of the resin particle after compression / release observed from a direction orthogonal to the compression direction is 1.1 or more.
  7. 　スペーサに用いられるか、電子部品用接着剤に用いられるか、導電部を有する導電性粒子を得るために用いられるか、又は、積層造形用材料に用いられる、請求項１～６のいずれか１項に記載の樹脂粒子。 Any one of claims 1 to 6, which is used as a spacer, as an adhesive for electronic parts, used for obtaining conductive particles having a conductive portion, or used as a material for laminated molding. The resin particles described in the section.
  8. 　液晶表示素子用スペーサとして用いられるか、電子部品用接着剤として用いられるか、又は、導電部を有する導電性粒子を得るために用いられる、請求項１～７のいずれか１項に記載の樹脂粒子。 The resin according to any one of claims 1 to 7, which is used as a spacer for a liquid crystal display element, an adhesive for an electronic component, or used for obtaining conductive particles having a conductive portion. particle.
  9. 　請求項１～８のいずれか１項に記載の樹脂粒子と、
    　前記樹脂粒子の表面上に配置された導電部とを備える、導電性粒子。     The resin particles according to any one of claims 1 to 8 and
    A conductive particle comprising a conductive portion arranged on the surface of the resin particle.
  10. 　前記導電部の外表面上に配置された絶縁性物質をさらに備える、請求項９に記載の導電性粒子。 The conductive particle according to claim 9, further comprising an insulating substance arranged on the outer surface of the conductive portion.
  11. 　前記導電部の外表面に突起を有する、請求項９又は１０に記載の導電性粒子。 The conductive particles according to claim 9 or 10, which have protrusions on the outer surface of the conductive portion.
  12. 　導電性粒子と、バインダー樹脂とを含み、
    　前記導電性粒子が、請求項１～８のいずれか１項に記載の樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備える、導電材料。     Contains conductive particles and binder resin,
    A conductive material in which the conductive particles include the resin particles according to any one of claims 1 to 8 and a conductive portion arranged on the surface of the resin particles.
  13. 　第１の接続対象部材と、
    　第２の接続対象部材と、
    　前記第１の接続対象部材と前記第２の接続対象部材とを接続している接続部とを備え、
    　前記接続部が、請求項１～８のいずれか１項に記載の樹脂粒子により形成されているか、又は前記樹脂粒子を含む組成物により形成されている、接続構造体。     The first member to be connected and
    The second connection target member and
    A connecting portion connecting the first connection target member and the second connection target member is provided.
    A connecting structure in which the connecting portion is formed of the resin particles according to any one of claims 1 to 8, or is formed of a composition containing the resin particles.
  14. 　第１の電極を表面に有する第１の接続対象部材と、
    　第２の電極を表面に有する第２の接続対象部材と、
    　前記第１の接続対象部材と前記第２の接続対象部材とを接続している接続部とを備え、
    　前記接続部が、導電性粒子により形成されているか、又は前記導電性粒子とバインダー樹脂とを含む導電材料により形成されており、
    　前記導電性粒子が、請求項１～８のいずれか１項に記載の樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備え、
    　前記第１の電極と前記第２の電極とが前記導電性粒子により電気的に接続されている、接続構造体。     A first connection target member having a first electrode on its surface,
    A second connection target member having a second electrode on the surface,
    A connecting portion connecting the first connection target member and the second connection target member is provided.
    The connecting portion is formed of conductive particles, or is formed of a conductive material containing the conductive particles and a binder resin.
    The conductive particles include the resin particles according to any one of claims 1 to 8 and a conductive portion arranged on the surface of the resin particles.
    A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.
PCT/JP2020/030184 2019-08-08 2020-08-06 Resin particle, electrically conductive particle, electrically conductive material, and connected structure WO2021025112A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003043495A (en) * 2001-08-03 2003-02-13 Soken Chem & Eng Co Ltd Secondarily deformed anisotropically adhesive spacer particle, manufacturing method therefor and display device using the particle
JP2017037070A (en) * 2015-08-10 2017-02-16 三菱化学株式会社 Separating agent and liquid chromatography column
WO2018230470A1 (en) * 2017-06-12 2018-12-20 積水化学工業株式会社 Resin particles, conductive particles, conductive material, adhesive, connection structure and liquid crystal display element
JP2019046801A (en) * 2017-09-06 2019-03-22 積水化学工業株式会社 Base material particle, conductive particle, conductive material and connection structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003043495A (en) * 2001-08-03 2003-02-13 Soken Chem & Eng Co Ltd Secondarily deformed anisotropically adhesive spacer particle, manufacturing method therefor and display device using the particle
JP2017037070A (en) * 2015-08-10 2017-02-16 三菱化学株式会社 Separating agent and liquid chromatography column
WO2018230470A1 (en) * 2017-06-12 2018-12-20 積水化学工業株式会社 Resin particles, conductive particles, conductive material, adhesive, connection structure and liquid crystal display element
JP2019046801A (en) * 2017-09-06 2019-03-22 積水化学工業株式会社 Base material particle, conductive particle, conductive material and connection structure

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