WO2021025113A1 - 樹脂粒子、導電性粒子、導電材料及び接続構造体 - Google Patents

樹脂粒子、導電性粒子、導電材料及び接続構造体 Download PDF

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Publication number
WO2021025113A1
WO2021025113A1 PCT/JP2020/030185 JP2020030185W WO2021025113A1 WO 2021025113 A1 WO2021025113 A1 WO 2021025113A1 JP 2020030185 W JP2020030185 W JP 2020030185W WO 2021025113 A1 WO2021025113 A1 WO 2021025113A1
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Prior art keywords
conductive
resin particles
particles
resin
compression
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PCT/JP2020/030185
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English (en)
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 JP2021537377A priority Critical patent/JPWO2021025113A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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

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 when released from compression, after compression release.
  • resin particles in which the resin particles of the above have two planar portions facing each other in the compression direction.
  • the ratio of the major axis of the flat portion of the resin particles after compression / release to the longest diameter of the resin particles after compression / release is 0.10 or more. It is 95 or less.
  • 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 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 when 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, the resin particles after compression and release are compressed. It has two plane portions that face each other in the direction. 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.
  • resin particles In the resin particles according to the present invention, when 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, the resin particles after compression and release are compressed. It has two plane portions that face each other in the direction.
  • 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 and can maintain a good compressed shape when heat-compressed. 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 when 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, the resin particles after compression and release are compressed. It has two plane portions that face each other in the direction.
  • the resin particles according to the present invention have different compression characteristics from the conventional resin particles.
  • a method of using resin particles having flexibility and low resilience can be mentioned.
  • 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 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.
  • 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 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 major axis of the flat portion of the resin particles after compression release.
  • B be the longest diameter of the resin particles after compression release.
  • A is the diameter of the plane portion.
  • B is the major axis of the resin particles 1 in the direction orthogonal to the compression direction P.
  • the major axis A of the surface of the resin particles after compression release and the longest diameter B of the resin particles after compression release can be calculated, for example, by observing the resin particles after compression release from a direction orthogonal to the compression direction. it can.
  • the ratio of A to B is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.30 or more. It is particularly preferably 0.40 or more, most preferably 0.60 or more, preferably 0.95 or less, more preferably 0.90 or less, still more preferably 0.85 or less, and particularly preferably 0.80 or less.
  • the above ratio (A / B) is preferably obtained by observing 50 arbitrary resin particles with an electron microscope or an optical microscope and calculating the average value of the ratio (A / B) of each resin particle.
  • 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 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 a direction orthogonal to the compression direction may be 1.1 or more, 1.3 or more, or 5 or less. It may be 3 or less, 2 or less, or 1.5 or less.
  • the aspect ratio of the resin particles after compression release indicates the major axis / minor axis of the resin particles observed from the direction orthogonal to the compression direction.
  • 50 arbitrary resin particles are observed with an electron microscope or an optical microscope, and the maximum and minimum diameters of the resin particles observed from the direction orthogonal to the compression direction are the major axes, respectively.
  • the minor axis by calculating the average value of the major axis / minor axis of each resin particle.
  • the aspect ratios are the first surface 1a (planar portion) and the second surface 1a (planar portion) of the longest diameter B of the resin particles after compression / release in the compression direction. Ratio to the distance to the surface 1b (planar portion) (distance between the first surface 1a (planar portion) and the second surface 1b (planar portion) in the longest diameter B of the resin particles after compression release / compression direction) Is.
  • a method of using resin particles having flexibility and low recoverability can be mentioned.
  • 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. Further, as a method for obtaining resin particles having flexibility and low resilience, there is also a method of reducing the degree of cross-linking of the resin used.
  • 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.
  • Example 11 At the time of producing the resin particles, the blending amount of 4,4'-diaminodiphenylmethane was changed from 4.25 parts by weight to 8.50 parts by weight. Further, the stirring at 68 ° C. for 1 hour was changed to the stirring at 78 ° C. for 1 hour. Further, the reaction conditions at 68 ° C. and 20 hours were changed to the reaction conditions at 78 ° C. and 20 hours. 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 12 When producing the resin particles, 0.80 parts by weight of norbornane diamine was used instead of 4.25 parts by weight of 4,4′-diaminodiphenylmethane. Further, the stirring at 68 ° C. for 1 hour was changed to the stirring at 45 ° C. for 1 hour. Further, the reaction conditions at 68 ° C. and 20 hours were changed to the reaction conditions at 45 ° C. and 20 hours. 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.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle size of resin particles Dn: Mean value of particle size of resin particles
  • 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 longest diameter B of the resin particles after compression / release is the major axis A of the flat portions of the resin particles after compression / release.
  • the ratio to (A / B) was calculated. As the above ratio (A / B), the average value of the ratio (A / B) of 50 arbitrary resin particles was adopted.
  • 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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PCT/JP2020/030185 2019-08-08 2020-08-06 樹脂粒子、導電性粒子、導電材料及び接続構造体 WO2021025113A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003043495A (ja) * 2001-08-03 2003-02-13 Soken Chem & Eng Co Ltd ２次変形異方接着性スペーサー粒子、その製造方法及びその粒子を用いる表示デバイス。
JP2017037070A (ja) * 2015-08-10 2017-02-16 三菱化学株式会社 分離剤及び液体クロマトグラフィー用カラム
WO2018230470A1 (ja) * 2017-06-12 2018-12-20 積水化学工業株式会社 樹脂粒子、導電性粒子、導電材料、接着剤、接続構造体及び液晶表示素子
JP2019046801A (ja) * 2017-09-06 2019-03-22 積水化学工業株式会社 基材粒子、導電性粒子、導電材料及び接続構造体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003043495A (ja) * 2001-08-03 2003-02-13 Soken Chem & Eng Co Ltd ２次変形異方接着性スペーサー粒子、その製造方法及びその粒子を用いる表示デバイス。
JP2017037070A (ja) * 2015-08-10 2017-02-16 三菱化学株式会社 分離剤及び液体クロマトグラフィー用カラム
WO2018230470A1 (ja) * 2017-06-12 2018-12-20 積水化学工業株式会社 樹脂粒子、導電性粒子、導電材料、接着剤、接続構造体及び液晶表示素子
JP2019046801A (ja) * 2017-09-06 2019-03-22 積水化学工業株式会社 基材粒子、導電性粒子、導電材料及び接続構造体

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