WO2014084173A1 - 絶縁性粒子付き導電性粒子、導電材料及び接続構造体 - Google Patents

絶縁性粒子付き導電性粒子、導電材料及び接続構造体 Download PDF

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WO2014084173A1
WO2014084173A1 PCT/JP2013/081661 JP2013081661W WO2014084173A1 WO 2014084173 A1 WO2014084173 A1 WO 2014084173A1 JP 2013081661 W JP2013081661 W JP 2013081661W WO 2014084173 A1 WO2014084173 A1 WO 2014084173A1
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Prior art keywords
particles
conductive
insulating
insulating particles
conductive particles
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PCT/JP2013/081661
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English (en)
French (fr)
Japanese (ja)
Inventor
茂雄 真原
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積水化学工業株式会社
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Priority to JP2013555500A priority Critical patent/JP5530571B1/ja
Priority to CN201380044989.XA priority patent/CN104584141B/zh
Priority to KR1020157001454A priority patent/KR102095291B1/ko
Publication of WO2014084173A1 publication Critical patent/WO2014084173A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients

Definitions

  • the present invention relates to conductive particles with insulating particles in which insulating particles are arranged on the surface of the conductive particles. Moreover, this invention relates to the electrically-conductive material and connection structure using the said electroconductive particle with an insulating particle.
  • Pasty or film anisotropic conductive materials are widely known.
  • anisotropic conductive material a plurality of conductive particles are dispersed in a binder resin or the like.
  • the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
  • FOG Glass
  • COF Chip on Film
  • conductive particles conductive particles with insulating particles in which insulating particles are arranged on the surface of the conductive particles may be used.
  • Patent Document 1 discloses conductive particles with insulating particles in which a part of the surface of the conductive particles is coated with insulating particles.
  • the mass of the insulating particles is 2/1000 to 26/1000 of the mass of the conductive particles.
  • the mass of the insulating particles is in the range of 9/1000 to 30/1000 of the mass of the conductive particles.
  • the L / S of the electrode width and the inter-electrode width has been further narrowed with the downsizing and high performance of electronic devices.
  • an electrode having a narrow L / S is conductively connected, it is difficult to arrange the conductive particles with insulating particles on the electrodes with high accuracy.
  • the dispersibility of the conductive particles with insulating particles is low in the anisotropic conductive material.
  • An object of the present invention is to provide conductive particles with insulating particles capable of efficiently disposing conductive particles on the electrodes when used for electrical connection between the electrodes, and conductive properties with the insulating particles.
  • An object is to provide a conductive material and a connection structure using particles.
  • a limited object of the present invention is to provide conductive particles with insulating particles capable of enhancing dispersibility in a conductive material, and conductive materials and connection structures using the conductive particles with insulating particles. That is.
  • the method includes: conductive particles having at least a conductive part on a surface thereof; and a plurality of insulating particles arranged on the surface of the conductive particles, wherein the weight of the entire insulating particles is Conductive particles with insulating particles having a ratio of the conductive particles to the weight of more than 0.03 and 0.25 or less are provided.
  • the conductive particles with insulating particles when the insulating particles are organic particles or inorganic particles, and the insulating particles are organic particles, the entire insulating particles
  • the conductive weight is the total weight of the insulating particles. The ratio to the weight of the particles is 0.08 or more and 0.25 or less.
  • the insulating particles are organic particles, and the ratio of the total weight of the insulating particles to the weight of the conductive particles is 0.03. It is 0.12 or less.
  • the insulating particles are inorganic particles, and the ratio of the weight of the whole insulating particles to the weight of the conductive particles is 0.08 or more. , 0.25 or less.
  • the conductive particles include base particles and a conductive portion disposed on the surface of the base particles.
  • the ratio of the total weight of the insulating particles to the weight of the base particles is more than 0.086 and less than 0.600.
  • the conductive particles have a plurality of protrusions on the surface of the conductive part.
  • the average particle diameter of the insulating particles is larger than the average height of the protrusions.
  • the conductive particles with insulating particles are dispersed in a binder resin and used as a conductive material.
  • the conductive particles with insulating particles are used for electrical connection between the electrodes, and the space in the portion where the electrodes are not formed is used.
  • the minimum value of the interelectrode width is 20 ⁇ m or less.
  • a conductive material including the conductive particles with insulating particles described above and a binder resin.
  • 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 A connecting portion connecting the second connection target member, wherein the connecting portion is formed of the above-described conductive particles with insulating particles, or the conductive particles with insulating particles and a binder resin.
  • a connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles. Is provided.
  • the minimum value of the inter-electrode width of the space where the first electrode is not formed and the electrode of the space where the second electrode is not formed is 20 ⁇ m or less.
  • the conductive particles with insulating particles according to the present invention include conductive particles having at least a conductive portion on a surface thereof, and a plurality of insulating particles arranged on the surface of the conductive particles, and further, the insulating material. Since the ratio of the total weight of the conductive particles to the weight of the conductive particles is more than 0.03 and 0.25 or less, the conductive particles with insulating particles according to the present invention are used for electrical connection between the electrodes. When used, the conductive particles can be efficiently disposed on the electrode.
  • FIG. 1 is a cross-sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing conductive particles with insulating particles according to the third embodiment of the present invention.
  • FIG. 4 is a front sectional view schematically showing a connection structure using conductive particles with insulating particles according to the first embodiment of the present invention.
  • FIG. 5 is a schematic diagram for explaining a method for evaluating the coverage.
  • the conductive particles with insulating particles according to the present invention include conductive particles having at least a conductive part on the surface, and a plurality of insulating particles arranged on the surface of the conductive particles.
  • the ratio of the weight X of the whole insulating particles to the weight Y of the conductive particles exceeds 0.03, 25 or less.
  • the conductive particles with insulating particles according to the present invention By adopting the above-described configuration in the conductive particles with insulating particles according to the present invention, particularly when the ratio (weight (X / Y)) exceeds 0.03, that is, the size of the insulating particles is relatively large. In addition, since the number of insulating particles is relatively large, excessive flow of the conductive particles with insulating particles is suppressed when obtaining a connection structure, and the conductive particles with insulating particles are efficiently applied on the electrodes. Can be arranged.
  • the electroconductive particle with an insulating particle is arrange
  • the conductive particles with insulating particles are aggregated. It becomes difficult to occur, and the dispersibility of the conductive particles with insulating particles increases. Furthermore, even if aggregates of conductive particles with insulating particles are generated in the conductive material, the aggregates of conductive particles with insulating particles can be separated into conductive particles with insulating particles by stirring the conductive material. It can be separated into active particles.
  • the electrode width which is the line (L) where the electrode is formed, and the space between the electrodes where the electrode is not formed (S)
  • the width is getting narrower.
  • the conventional conductive material has a problem that insulation defects are particularly likely to occur because many conductive particles with insulating particles are easily arranged in the space (S). There is.
  • the use of the conductive particles with insulating particles according to the present invention makes it difficult for the conductive particles to be disposed in the space (S), and it is possible to effectively suppress the occurrence of poor insulation.
  • the weight of the insulating particles is relatively large, the insulation is effectively enhanced, and even when the conductive electrodes are connected between fine electrodes having L / S of 20 ⁇ m or less / 20 ⁇ m or less, the insulation reliability Can be made high enough.
  • the insulation reliability can be effectively increased, and the L / S is When it is 20 ⁇ m or less / 20 ⁇ m or less, the insulation reliability can be further effectively improved, and when L / S is 17.5 ⁇ m or less / 17.5 ⁇ m or less, the insulation reliability is even more effective.
  • L / S is 15 ⁇ m or less / 15 ⁇ m or less, the insulation reliability can be particularly effectively increased.
  • the L / S may be 50 ⁇ m or less / 50 ⁇ m or less.
  • the width of the electrode which is the line (L) of the portion where the electrodes (first and second electrodes) are formed.
  • the minimum value is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 17.5 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the electrode width of the line (L) is preferably larger than the average particle size of the conductive particles with insulating particles, more preferably 1.1 times or more the average particle size of the conductive particles. More preferably, it is more than twice, and it is particularly preferably 3 times or more.
  • the electrode width of the line (L) may be 50 ⁇ m or less.
  • the interelectrode width which is a space (S) in a portion where the electrodes (first and second electrodes) are not formed.
  • the minimum value of is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 17.5 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the width between the electrodes as the space (S) is preferably larger than the average particle diameter of the conductive particles in the conductive particles with insulating particles, and more than 1.1 times the average particle diameter of the conductive particles. Is more preferably 2 times or more, and particularly preferably 3 times or more.
  • the inter-electrode width that is the space (S) may be 50 ⁇ m or less.
  • the conductive particles with insulating particles according to the present invention is used for electrical connection between the electrodes, It is preferable that the minimum value of the width between electrodes, which is a space in a portion where the electrodes are not formed, is 20 ⁇ m or less.
  • the above ratio (weight ratio (X / Y)) is preferably 0.031 or more.
  • the above ratio (weight ratio (X / Y)) is preferably 0.2 or less, more preferably 0.15 or less, and still more preferably 0. .12 or less.
  • the insulating particles are preferably organic particles or inorganic particles.
  • the ratio (weight ratio (X / Y)) is preferably more than 0.03, and preferably 0.12 or less.
  • the ratio (weight ratio (X / Y)) is preferably 0.08 or more, and preferably 0.25 or less.
  • the insulating particles are organic particles, and the ratio (weight ratio (X / Y)) exceeds 0.03 and is 0.12 or less.
  • the insulating particles are inorganic particles and the ratio (weight ratio (X / Y)) is 0.08 or more and 0.25 or less.
  • the conductive particles are formed on the surface of the base material particles and the base material particles. It is preferable to have a conductive part arranged.
  • the conductive part is preferably a conductive layer. Further, by using conductive particles having base particles and conductive portions arranged on the surfaces of the base particles, the above ratio (weight ratio (X / Y)) and a ratio described later (weight ratio (X / Z)) can be easily controlled within a suitable range.
  • the weight X of the entire insulating particles The ratio of the above base particles to the weight Z (weight ratio (X / Z)) exceeds 0.086, preferably 0.089 or more. From the viewpoint of easily producing conductive particles with insulating particles, the ratio (weight ratio (X / Z)) is preferably less than 0.600, more preferably 0.590 or less, and still more preferably 0.560. It is as follows.
  • the above ratio (weight ratio (X / Y)) and the above ratio (weight ratio (X / Z)) are further determined depending on the types of materials used for the insulating particles, the conductive part and the base material particles. And it can adjust suitably with the magnitude
  • the ratio (weight ratio (X / Z)) preferably exceeds 0.086, preferably 0.350 or less.
  • the ratio (weight ratio (X / Z)) is preferably 0.200 or more, and preferably 0.590 or less.
  • the insulating particles are organic particles, and the ratio (weight ratio (X / Z)) exceeds 0.086 and is 0.350 or less.
  • the insulating particles are inorganic particles, and the ratio (weight ratio (X / Z)) is preferably 0.200 or more and less than 0.600, preferably 0.200 or more, 0 More preferably, it is 590 or less.
  • the coverage which is the area of the portion covered with the insulating particles in the entire surface area of the conductive particles, is preferably 30% or more, more preferably 50% or more, still more preferably more than 50%, particularly preferably. 60% or more. When the coverage is equal to or higher than the lower limit, adjacent conductive particles are more difficult to contact.
  • the coverage is preferably 95% or less, more preferably 90% or less, still more preferably 80% or less, and particularly preferably 70% or less. If the coverage is less than or equal to the above upper limit, the insulating particles can be sufficiently eliminated without applying heat and pressure more than necessary when the electrodes are connected.
  • the coverage is obtained as follows.
  • the coverage X1 is the area (projected area) of the portion covered with the insulating particles in the entire surface area of the conductive particles.
  • the outer surface of the conductive portion of the conductive particles A with insulating particles A with insulating particles is present in the circle on the (outer peripheral edge), and the insulating particle B2 present on the circumference on the outer surface (outer peripheral edge) of the conductive portion of the conductive particle A with insulating particles is 0.00.
  • Count as 5. The said coverage is shown by the ratio of the projection area of an insulating particle with respect to the projection area of the electroconductive particle A with an insulating particle.
  • Coverage (%) (((number of insulating particles in circle) ⁇ 1 + (number of insulating particles on the circumference) ⁇ 0.5) ⁇ projection area of insulating particles) / (with insulating particles) Projected area of conductive particles)) ⁇ 100 (1)
  • the conductive particles with insulating particles according to the present invention are preferably dispersed in a binder resin and used as a conductive material.
  • the conductive particles with insulating particles according to the present invention are preferably used for a paste-like conductive paste.
  • the conductive material is preferably a conductive paste.
  • the conductive particles with insulating particles according to the present invention are preferably used for a conductive paste having a viscosity at 25 ° C. and 2.5 rpm of more than 100 Pa ⁇ s and 1000 Pa ⁇ s or less.
  • the viscosity of the conductive paste at 25 ° C. and 2.5 rpm is preferably more than 100 Pa ⁇ s and 1000 Pa ⁇ s or less.
  • the variation coefficient of the particle diameter of the conductive particles with insulating particles is preferably 8% or less, more preferably 5% or less.
  • the coefficient of variation (CV value) is expressed by the following equation.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of conductive particles with insulating particles Dn: Average value of particle diameter of conductive particles with insulating particles
  • the conductive particles with insulating particles include an insulating property that can be adsorbed on the surface of the conductive particles via a polymer electrolyte that can adsorb the polar groups on the surface of the conductive particles.
  • Conductive particles with insulating particles in which the particles are disposed are included.
  • the conductive particles with insulating particles may be obtained by electrostatically adsorbing the polymer electrolyte on at least a part of the surface of the conductive particles and then further electrostatically adsorbing the insulating particles. Is obtained.
  • FIG. 1 is a sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention.
  • a conductive particle 1 with insulating particles shown in FIG. 1 includes a conductive particle 2 and a plurality of insulating particles 3 arranged on the surface of the conductive particle 2.
  • the insulating particles 3 are attached to the surface of the conductive particles 2.
  • the insulating particles 3 are made of an insulating material.
  • the insulating particles 3 are not coated particles. Insulating particles 43 described later may be used instead of the insulating particles 3.
  • the conductive particle 2 includes a base particle 11 and a conductive portion 12 disposed on the surface of the base particle 11.
  • the conductive part 12 is a conductive layer.
  • the conductive part 12 covers the surface of the base particle 11.
  • the conductive particle 2 is a coated particle in which the surface of the base particle 11 is coated with the conductive portion 12.
  • the conductive particle 2 has a conductive portion 12 on the surface.
  • FIG. 2 is a sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention.
  • a conductive particle 21 with insulating particles shown in FIG. 2 includes conductive particles 22 and a plurality of insulating particles 3 arranged on the surface of the conductive particles 22.
  • the insulating particles 3 are attached to the surface of the conductive particles 22. Insulating particles 43 described later may be used instead of the insulating particles 3.
  • the conductive particle 22 includes the base particle 11 and a conductive portion 31 disposed on the surface of the base particle 11.
  • the conductive part 31 is a conductive layer.
  • the conductive particles 22 have a plurality of core substances 32 on the surface of the substrate particles 11.
  • the conductive portion 31 covers the base particle 11 and the core substance 32.
  • the conductive particles 22 have a plurality of protrusions 33 on the surface.
  • the surface of the conductive portion 31 is raised by the core substance 32, and a plurality of protrusions 33 are formed.
  • FIG. 3 the electroconductive particle with an insulating particle which concerns on the 3rd Embodiment of this invention is shown with sectional drawing.
  • a conductive particle 41 with insulating particles shown in FIG. 3 includes conductive particles 42 and a plurality of insulating particles 43 arranged on the surface of the conductive particles 42. Insulating particles 43 are attached to the surface of the conductive particles 42. The insulating particles 3 may be used instead of the insulating particles 43.
  • the conductive particle 42 includes the base particle 11 and a conductive portion 51 disposed on the surface of the base particle 11.
  • the conductive part 51 is a conductive layer.
  • the conductive particles 42 do not have a core substance like the conductive particles 22.
  • the conductive portion 51 has a first portion and a second portion that is thicker than the first portion.
  • the conductive particles 42 have a plurality of protrusions 52 on the surface. A portion excluding the plurality of protrusions 52 is the first portion of the conductive portion 51.
  • the plurality of protrusions 52 are the second portions where the conductive portion 51 is thick.
  • the insulating particles 43 are coated particles.
  • the insulating particles 43 have an insulating particle main body 45 and a layer 46 covering the surface of the insulating particle main body 45.
  • the layer 46 is preferably formed of an organic compound, and is preferably formed of a polymer compound.
  • the layer 46 covers the entire surface of the insulating particle body 5. Therefore, the layer 46 is disposed between the conductive particles 42 and the insulating particle main body 45. The layer 46 may be present so as to cover at least a part of the surface of the insulating particle body, and does not need to cover the entire surface of the insulating particle body. The layer 46 is preferably disposed between the conductive particles and the insulating particle body.
  • the ratio of the weight X of the entire insulating particles 3, 43 to the weight Y of the conductive particles 2, 22, 42 is 0 0.03 and 0.25 or less.
  • the conductive particles 2, 22, 42 can be efficiently arranged on the electrodes.
  • aggregation of the conductive particles 1, 21, 41 with insulating particles hardly occurs, and the dispersibility of the conductive particles 1, 21, 41 with insulating particles increases.
  • Conductive particles with insulating particles can be obtained by disposing the insulating particles on the surface of the conductive particles having at least a conductive portion on the surface.
  • the conductive part in the conductive particles is preferably a conductive layer.
  • the said electroconductive particle should just have an electroconductive part on the surface at least.
  • the conductive particles are preferably conductive particles having base particles and conductive portions arranged on the surface of the base particles.
  • the substrate particles are preferably substrate particles excluding metal particles, and more preferably resin particles, inorganic particles excluding metal, or organic-inorganic hybrid particles.
  • the substrate particles are preferably resin particles formed of a resin.
  • the conductive particles with insulating particles are compressed by placing the conductive particles with insulating particles between the electrodes and then pressing them.
  • the substrate particles are resin particles, the conductive particles are likely to be deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction
  • the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonate , Polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide , Polyacetal, polyimide, polyamideimide, polyether ether Tons, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer,
  • polyolefin resins such as polyethylene, polypropylene,
  • the divinylbenzene copolymer examples include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.
  • the monomer having the ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. And a polymer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (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 ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure Silane-
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
  • the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal
  • examples of inorganic substances for forming the substrate particles include silica and carbon black.
  • the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary.
  • grains obtained by performing are mentioned.
  • the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the metal for forming the conductive part is not particularly limited.
  • the metal include gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, tungsten, and molybdenum. , Silicon and alloys thereof.
  • the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes becomes still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable.
  • hydroxyl groups are present on the surface of the conductive part due to oxidation.
  • a hydroxyl group exists on the surface of a conductive portion formed of nickel by oxidation.
  • Such a conductive portion having a hydroxyl group is easily chemically bonded to the insulating particles, for example, chemically bonded to the insulating particles having a hydroxyl group.
  • the conductive part may be formed of one layer.
  • the conductive part may be formed of a plurality of layers. That is, the conductive part 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 the gold layer or the palladium layer Is more preferable, and a gold layer is particularly preferable.
  • the outermost layer is these preferred conductive portions, the connection resistance between the electrodes is further reduced.
  • the outermost layer is a gold layer, the corrosion resistance is further enhanced.
  • the method for forming the conductive portion on the surface of the substrate particle is not particularly limited.
  • a method for forming the conductive portion for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc.
  • the method by electroless plating is preferable.
  • the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
  • a method for forming a conductive part on the surface of the substrate particle a method by physical collision is also effective from the viewpoint of improving productivity.
  • a method of forming by physical collision for example, there is a method of coating using a theta composer (manufactured by Tokuju Kogakusha Co., Ltd.).
  • the average particle diameter of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the contact area between the conductive particles and the electrodes is sufficiently large when the electrodes are connected using the conductive particles with insulating particles.
  • the “average particle size” of the conductive particles indicates a number average particle size.
  • the average particle diameter of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
  • the thickness of the conductive part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.3 ⁇ m or less.
  • the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles are not hardened, and the conductive particles are sufficiently deformed when connecting the electrodes. .
  • the thickness of the conductive part of the outermost layer is preferably 0.001 ⁇ m or more, particularly when the outermost layer is a gold layer. More preferably, it is 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably 0.1 ⁇ m or less.
  • the thickness of the conductive portion of the outermost layer is not less than the above lower limit and not more than the above upper limit, the coating with the conductive portion of the outermost layer can be made uniform, the corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficiently high Lower.
  • the thickness of the conductive part can be measured by observing the cross section of the conductive particles or the conductive particles with insulating particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the conductive particles preferably have a plurality of protrusions on the conductive surface.
  • the conductive portion preferably has a plurality of protrusions on the surface (outer surface).
  • An oxide film is often formed on the surface of the electrode connected by the conductive particles with insulating particles. Furthermore, an oxide film is often formed on the surface of the conductive part of the conductive particles.
  • a method of forming a conductive portion by electroless plating after attaching a core substance to the surface of the base particle, conductive by electroless plating on the surface of the base particle.
  • the core material is attached, and further, the conductive material is formed by electroless plating, and the core material is electrolessly plated in the middle of forming the conductive portion by electroless plating on the surface of the base particle.
  • the method of adding in a liquid is mentioned.
  • the core material is not necessarily used to form the protrusions.
  • the protrusion can also be formed by partially varying the thickness of the conductive portion.
  • the conductive particles may have a first conductive part on the surface of the base particle, and may have a second conductive part on the surface of the first conductive part.
  • a core substance may be attached to the surface of the first conductive part. It is preferable that the core substance is covered with the second conductive portion.
  • the thickness of the first conductive portion is preferably 0.05 ⁇ m or more, and preferably 0.5 ⁇ m or less.
  • the conductive particles form a first conductive part on the surface of the base particle, and then attach a core substance on the surface of the first conductive part, and then the first conductive part and the core substance It is preferable to be obtained by forming the second conductive portion on the surface.
  • the material constituting the core material there may be mentioned a conductive material and a non-conductive material.
  • the conductive material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers.
  • the conductive polymer include polyacetylene.
  • the nonconductive material include silica, alumina, and zirconia. Among them, metal is preferable because conductivity can be increased.
  • the core substance is preferably metal particles.
  • the metal examples include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead.
  • examples thereof include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and tungsten carbide. Of these, nickel, copper, silver or gold is preferable.
  • the metal constituting the core substance may be the same as or different from the metal constituting the conductive part.
  • the shape of the core substance is not particularly limited.
  • the shape of the core substance is preferably a lump.
  • Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
  • the insulating particles are particles having insulating properties.
  • the insulating particles are preferably smaller than the conductive particles.
  • the insulating particles can prevent a short circuit between adjacent electrodes.
  • the insulating particle between an electroconductive part and an electrode can be easily excluded by pressurizing the electroconductive particle with an insulating particle with two electrodes in the case of the connection between electrodes.
  • the protrusion is provided on the surface of the conductive portion, the insulating particles between the conductive portion and the electrode can be easily removed. Furthermore, since the protruding portion facilitates contact with the electrode, connection reliability is improved.
  • Examples of the material constituting the insulating particles include an insulating resin and an insulating inorganic substance.
  • the insulating resin the said resin quoted as resin for forming the resin particle which can be used as a base particle is mentioned.
  • As said insulating inorganic substance the said inorganic substance quoted as an inorganic substance for forming the inorganic particle which can be used as a base particle is mentioned.
  • the insulating particles are preferably organic particles or inorganic particles.
  • the organic particles are formed using an organic compound (for example, an insulating resin).
  • the inorganic particles are formed using an inorganic compound.
  • the insulating resin that is the material of the insulating particles include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, heat Examples thereof include curable resins and water-soluble resins.
  • thermoplastic resin examples include vinyl polymers and vinyl copolymers.
  • thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
  • the insulating particles preferably have an insulating particle body and a layer covering at least a partial region of the surface of the insulating particle body.
  • the insulating particles are more difficult to be detached from the surface of the conductive particles by kneading in the production of the conductive material.
  • the insulating particles are difficult to be detached from the surface of the conductive particles.
  • the material of the insulating particles or the insulating particle main body is preferably an inorganic compound, and the insulating particles or the insulating particle main body is Inorganic particles are preferred.
  • the layer covering at least a part of the surface of the insulating particle main body is preferably formed of an organic compound.
  • the compound is preferably a polymer compound.
  • grains by which the surface of the inorganic particle is covered with the layer formed with the organic compound is called an inorganic particle in this specification.
  • an organic particle a particle in which the surface of the organic particle is covered with a layer formed of an organic compound is referred to as an organic particle.
  • the inorganic particles are particles in which most (for example, 80% by weight or more) is formed of an inorganic compound.
  • the organic particles are particles that are mostly formed of an organic compound (for example, 80% by weight or more).
  • the conductive particles with insulating particles have a layer formed of a polymer compound using a polymer compound or a compound that becomes a polymer compound so as to cover at least a part of the surface of the insulating particle body. It is preferably obtained through a step of forming and obtaining insulating particles and a step of obtaining the conductive particles with insulating particles by attaching the insulating particles to the surfaces of the conductive particles having at least the conductive portion on the surface. .
  • the insulating particles or the insulating particle main body is preferably inorganic particles, and is preferably silica particles.
  • the inorganic particles include shirasu particles, hydroxyapatite particles, magnesia particles, zirconium oxide particles, aluminum oxide particles, silicon carbide particles, silicon nitride particles, aluminum nitride particles, and silica particles.
  • the silica particles include pulverized silica and spherical silica, and spherical silica is preferably used.
  • the silica particles preferably have a functional group capable of chemical bonding such as a carboxyl group and a hydroxyl group on the surface, and more preferably have a hydroxyl group.
  • Inorganic particles are relatively hard, especially silica particles are relatively hard.
  • conductive particles with insulating particles using such hard insulating particles as insulating particles are added to a binder resin and kneaded, the insulating particles are hard, so that the insulating particles are removed from the surface of the conductive particles. There is a tendency to detach easily.
  • the insulating particles have a layer formed of the polymer compound, even if hard insulating particles are used, it is possible to suppress the separation of the hard insulating particles during the kneading.
  • the layer formed of the organic compound and the layer formed of the polymer compound serve as a flexible layer, for example.
  • the polymer compound in the layer formed of the polymer compound or the compound that becomes the polymer compound by polymerization or the like is preferably a compound having a polymerizable reactive functional group.
  • the polymerizable reactive functional group is preferably an unsaturated double bond.
  • a compound having an unsaturated double bond (a compound that becomes a polymer compound) may be subjected to a polymerization reaction on the surface of the insulating particle main body, and the reactive functional group on the surface of the polymer compound and the insulating particle main body. And may be reacted.
  • the polymer compound examples include a compound having a (meth) acryloyl group, a compound having an epoxy group, and a compound having a vinyl group.
  • the polymer compound or the compound to be the polymer compound is (meth) It preferably has at least one reactive functional group selected from the group consisting of an acryloyl group, a glycidyl group and a vinyl group.
  • the polymer compound or the compound to be the polymer compound preferably has a (meth) acryloyl group.
  • Specific examples of the compound having the (meth) acryloyl group include methacrylic acid, hydroxyethyl acrylate, and ethylene glycol dimethacrylate.
  • epoxy compound examples include bisphenol A type epoxy resin and resorcinol glycidyl ether.
  • Specific examples of the compound having a vinyl group include styrene and vinyl acetate.
  • the average particle size of the insulating particles can be appropriately selected depending on the particle size of the conductive particles, the use of the conductive particles with insulating particles, and the like.
  • the average particle diameter of the insulating particles is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 2.5 ⁇ m or less, still more preferably 1 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less. It is.
  • the average particle diameter of the insulating particles is not less than the above lower limit, the conductive particles in the plurality of conductive particles with insulating particles are difficult to contact when the conductive particles with insulating particles are dispersed in the binder resin. Become.
  • the average particle diameter of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating particles between the electrodes and the conductive particles when connecting the electrodes, There is no need to heat to high temperatures.
  • the “average particle size” of the insulating particles indicates the number average particle size.
  • the average particle size of the insulating particles is determined using a particle size distribution measuring device or the like.
  • the average particle diameter of the insulating particles is preferably 1/2 or less of the particle diameter of the conductive particles, more preferably 1/3 or less, still more preferably 1/4 or less. / 5 or less is particularly preferable.
  • the particle diameter of the insulating particles is preferably 1/1000 or more of the particle diameter of the conductive particles, more preferably 1/10 or more, and even more preferably more than 1/10.
  • the average particle diameter of the insulating particles is 1/5 or less of the particle diameter of the conductive particles, for example, when producing conductive particles with insulating particles, the insulating particles are more efficient on the surface of the conductive particles. Adheres.
  • the average particle diameter of the insulating particles is preferably 0.5 times or more, more preferably 1 or more times the thickness of the conductive part (conductive layer) in the conductive particles.
  • the average particle diameter of the insulating particles is preferably 20 times or less, more preferably 10 times or less the thickness of the conductive part (conductive layer) in the conductive particles.
  • the average particle size of the insulating particles is preferably larger than the average particle size of the core substance, and more preferably 1.1 times or more.
  • the average particle size of the insulating particles is preferably 20 times or less, more preferably 10 times or less, the average particle size of the core substance.
  • the “average particle size” of the core material indicates the number average particle size.
  • the average particle size of the core substance is determined using a particle size distribution measuring device or the like.
  • the average particle diameter of the insulating particles is preferably larger than the average height of the protrusions, and more preferably 1.1 times or more.
  • the average particle diameter of the insulating particles is preferably 20 times or less, more preferably 10 times or less the height of the protrusion.
  • the average height of the protrusions is an average of the heights of a plurality of protrusions.
  • the coefficient of variation (CV value) of the particle diameter of the insulating particles is preferably 1% or more, preferably 10% or less, more preferably 8% or less.
  • Two or more kinds of insulating particles having different particle diameters may be used.
  • the average particle size of the small insulating particles is preferably 1/2 or less of the average particle size of the large insulating particles.
  • the number of small insulating particles is preferably 1 ⁇ 4 or less of the number of large insulating particles.
  • the conductive material according to the present invention includes the above-described conductive particles with insulating particles and a binder resin. When the conductive particles with insulating particles are used, the insulating particles are unlikely to be detached from the surface of the conductive particles when the conductive particles with insulating particles are dispersed in the binder resin.
  • the conductive material according to the present invention is preferably an anisotropic conductive material.
  • the binder resin is not particularly limited. In general, an insulating resin is used as the binder resin.
  • the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder resin, only 1 type may be used and 2 or more types may be used together.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
  • examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin.
  • examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin.
  • 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 product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, and heat stability.
  • Various additives such as an agent, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
  • the method for dispersing the conductive particles with insulating particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used.
  • a method for dispersing the conductive particles with insulating particles in the binder resin for example, the conductive particles with insulating particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like.
  • a method a method in which the conductive particles with insulating particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, then added to the binder resin, and kneaded and dispersed with a planetary mixer or the like; and Examples include a method of diluting the binder resin with water or an organic solvent, adding the conductive particles with insulating particles, and kneading and dispersing with a planetary mixer or the like.
  • the conductive material can be used as a conductive paste and a conductive film.
  • the conductive paste may be a conductive ink or a conductive adhesive.
  • the conductive film includes a conductive sheet.
  • the conductive material including the conductive particles with insulating particles is a conductive film, a film not including the conductive particles with insulating particles is laminated on the conductive film including the conductive particles with insulating particles. May be.
  • the conductive material according to the present invention is preferably in a paste form, and is preferably a conductive paste.
  • the paste form includes liquid.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 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 with insulating particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is more It gets even higher.
  • the content of the conductive particles with insulating particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 40% by weight or less, more preferably 20%. % By weight or less, more preferably 10% by weight or less.
  • the content of the conductive particles with insulating particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.
  • connection structure can be obtained by connecting the connection target member using the conductive material including the conductive particles with insulating particles according to the present invention and the binder resin.
  • connection structure 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, the first connection target member, and the second The connection part which has connected the connection object member.
  • the connecting portion is formed of a conductive material including the conductive particles with insulating particles and the binder resin described above. The first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles.
  • FIG. 4 is a front sectional view schematically showing a connection structure using conductive particles with insulating particles according to the first embodiment of the present invention.
  • a connection structure 81 shown in FIG. 4 includes a first connection target member 82, a second connection target member 83, and a connection portion 84 connecting the first and second connection target members 82 and 83.
  • the connecting portion 84 is formed of a conductive material including the conductive particles 1 with insulating particles.
  • the connecting portion 84 is preferably formed by curing a conductive material including a plurality of conductive particles 1 with insulating particles.
  • the conductive particles 1 with insulating particles are schematically shown for convenience of illustration. Instead of the conductive particles 1 with insulating particles, conductive particles 21 and 41 with insulating particles may be used.
  • the first connection target member 82 has a plurality of first electrodes 82a on the surface (upper surface).
  • the second connection target member 83 has a plurality of second electrodes 83a on the surface (lower surface).
  • the 1st electrode 82a and the 2nd electrode 83a are electrically connected by the electroconductive particle 2 in the electroconductive particle 1 with one or some insulating particle. Therefore, the first and second connection target members 82 and 83 are electrically connected by the conductive particles 2 in the conductive particles 1 with insulating particles.
  • the manufacturing method of the connection structure is not particularly limited.
  • the conductive material is disposed between the first connection target member and the second connection target member to obtain a laminate, and then the laminate is heated and pressurized. Methods and the like.
  • the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120 to 220 ° C.
  • the insulating particles 3 existing between the conductive particles 2 and the first and second electrodes 82a and 83a can be eliminated.
  • the insulating particles 3 existing between the conductive particles 2 and the first and second electrodes 82a and 83a are melted or deformed, The surface of the conductive particle 2 is partially exposed. Note that a large force is applied during the heating and pressurization, so that some of the insulating particles 3 are peeled off from the surface of the conductive particles 2 and the surface of the conductive particles 2 is partially exposed.
  • the portion where the surface of the conductive particle 2 is exposed contacts the first and second electrodes 82a and 83a, so that the first and second electrodes 82a and 83a are electrically connected through the conductive particle 2. it can.
  • connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards.
  • the conductive material is preferably a conductive material for connecting electronic components.
  • the conductive material is preferably a conductive material for circuit connection.
  • the conductive material is a paste-like conductive paste, and is preferably applied on the connection target member in a paste-like state.
  • the conductive particles with insulating particles according to the present invention are, in particular, COG having a glass substrate and a semiconductor chip as connection target members, FOB or glass substrate having a glass epoxy substrate and a flexible printed circuit board (FPC) as connection target members.
  • a flexible printed circuit board (FPC) are suitably used for FOGs, and may be used for COG or FOG, or may be used for FOB or FOG.
  • the conductive particles with insulating particles according to the present invention may be used for COG, FOB, or FOG.
  • the first and second connection target members are a glass substrate and a semiconductor chip, a glass epoxy substrate and a flexible printed substrate, or a glass substrate and a flexible printed substrate. It is preferable that The first and second connection target members may be a glass substrate and a semiconductor chip, a glass epoxy substrate and a flexible printed substrate, or a glass substrate and a flexible printed substrate. .
  • bumps are provided on a semiconductor chip used in a COG having a glass substrate and a semiconductor chip as connection target members.
  • the bump size is preferably an electrode area of 1000 ⁇ m 2 or more and 10,000 ⁇ m 2 or less.
  • the electrode space in the semiconductor chip provided with the bump (electrode) is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and still more preferably 10 ⁇ m or less.
  • the conductive particles with insulating particles according to the present invention are preferably used.
  • the electrode space is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
  • the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
  • the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material for 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 following conductive particles A to G were prepared.
  • the conductive particles having a plurality of protrusions on the surface of the conductive layer were formed by arranging a plurality of nickel fine particles between the divinylbenzene resin particles and the nickel plating layer.
  • a nickel plating layer (conductive layer, thickness 0.08 ⁇ m) is formed on the surface of divinylbenzene resin particles (average particle diameter 2.78 ⁇ m), and a gold layer (conductive layer, thickness 0) is formed on the surface of the nickel plating layer.
  • Conductive particles C (the surface of the conductive layer has no protrusions, average particle diameter of 3.00 ⁇ m)
  • Conductive particles D having a nickel plating layer (conductive layer, thickness of 0.11 ⁇ m) formed on the surface of divinylbenzene resin particles (average particle size 2.78 ⁇ m) (a plurality of protrusions (average height) on the surface of the conductive layer) 0.1 ⁇ m), with an average particle size of 3.00 ⁇ m)
  • Conductive particles E having a nickel plating layer (conductive layer, thickness 0.125 ⁇ m) formed on the surface of divinylbenzene resin particles (average particle size 2.78 ⁇ m) (a plurality of protrusions (average height) on the surface of the conductive layer) 0.1 ⁇ m) with an average particle size of 3.03 ⁇ m)
  • a nickel plating layer (conductive layer, thickness 0.08 ⁇ m) is formed on the surface of divinylbenzene resin particles (average particle diameter 2.78 ⁇ m), and a gold layer (conductive
  • conductive particles F (average particle diameter of 3.00 ⁇ m having a plurality of protrusions (average height of 0.2 ⁇ m) on the surface of the conductive layer)
  • Conductive particles G having a nickel plating layer (conductive layer, thickness of 0.11 ⁇ m) formed on the surface of divinylbenzene resin particles (average particle diameter of 2.28 ⁇ m) (a plurality of protrusions (average height) on the surface of the conductive layer) 0.1 ⁇ m) with an average particle size of 2.50 ⁇ m)
  • insulating particles a average particle size 250 nm
  • Insulating particles b average particle size 180 nm
  • insulating particles c average particle size 350 nm
  • the following insulating particles d to f were prepared.
  • Insulating particles d (average particle size 400 nm), which are silica particles produced by the sol-gel method
  • Insulating particles e (average particle size 150 nm), which are silica particles produced by the sol-gel method
  • Insulating particles f (average particle size 500 nm), which are silica particles produced by the sol-gel method
  • the obtained insulating particles a to f were each dispersed in distilled water to obtain a 10 wt% dispersion of the insulating particles a to f.
  • Example 1 Conductive particles A having no protrusions on the surface of the conductive part and a 10 wt% dispersion of insulating particles a were prepared.
  • Example 1 After dispersing 50 parts by weight of conductive particles A in 300 mL of distilled water, a 10% by weight dispersion of insulating particles a was added dropwise and stirred at 50 ° C. for 8 hours to obtain a stirring liquid. The obtained stirring liquid was filtered, washed with methanol, and vacuum dried at 50 ° C. for 7 hours to obtain conductive particles with insulating particles.
  • the coverage was adjusted by the amount of the 10% by weight dispersion of the insulating particles a to f.
  • the coverage X1, the ratio (weight ratio (X / Y)) and the ratio (weight ratio (X / Z)) of the obtained conductive particles with insulating particles are shown in Table 1 below.
  • Example 2 to 7 and Comparative Examples 1 and 2 Insulation was conducted in the same manner as in Example 1 except that the types of conductive particles and insulating particles were changed as shown in Table 1 below, and the coverage X1 was set as shown in Table 1 below. Conductive particles with conductive particles were obtained.
  • Example 8 Conductive particles D having protrusions on the surface of the conductive portion and a 10 wt% dispersion of insulating particles a were prepared.
  • Table 2 below shows the coverage X1, the ratio (weight ratio (X / Y)), and the ratio (weight ratio (X / Z)) of the obtained conductive particles with insulating particles.
  • Example 9 to 15 and Comparative Examples 3 and 4 Insulation was carried out in the same manner as in Example 8 except that the types of conductive particles and insulating particles were changed as shown in Table 2 below, and the coverage X1 was set as shown in Table 2 below. Conductive particles with conductive particles were obtained.
  • weight ratios shown in Tables 1 and 2 below are measured values. However, the weight ratio can also be obtained by the following weight ratio calculation method. In the examples of the present application and the comparative example, the actual measurement value and the value obtained by the following calculation method of the weight ratio were in agreement.
  • the weight of one conductive particle is calculated from the specific gravity, the thickness and volume of the conductive part. Also, the number of insulating particles per conductive particle with insulating particles is calculated from the coverage ratio (covering density), etc., and the number of insulating particles per conductive particle with insulating particles is insulative. The specific gravity of the particles is taken as the total weight of the insulating particles per conductive particle with insulating particles. Calculate the weight ratio of each.
  • An anisotropic conductive material layer was formed on the upper surface of the glass substrate by coating the anisotropic conductive paste immediately after fabrication to a thickness of 20 ⁇ m.
  • the semiconductor chip was stacked on the upper surface of the anisotropic conductive material layer so that the electrodes face each other.
  • a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 3.0 MPa is applied to apply the anisotropic conductive material.
  • the material layer was cured at 185 ° C. to obtain a first connection structure.
  • 2nd connection structure was obtained like manufacture of the 1st connection structure except having used the above-mentioned glass substrate and semiconductor chip from which L / S differs.
  • 3rd connection structure was obtained like manufacture of the 1st connection structure except having used the above-mentioned glass substrate and semiconductor chip from which L / S differs.
  • Viscosity The viscosity of the obtained conductive material (anisotropic conductive paste) was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 2.5 rpm. The viscosity was determined according to the following criteria.
  • Ratio of the number of conductive particles arranged on the electrode is 70% or more
  • Ratio of the number of conductive particles arranged on the electrode is 60% or more and less than 70%
  • On the electrode Ratio of the number of conductive particles arranged is 50% or more and less than 60%
  • Ratio of the number of conductive particles arranged on the electrode is less than 50%
  • connection resistance between the upper and lower electrodes was measured by the four-terminal method, respectively. .
  • the average value of connection resistance was calculated. Note that the connection resistance can be obtained by measuring the voltage when a constant current is passed from the relationship of voltage current ⁇ resistance. The conduction reliability was determined according to the following criteria.
  • Example 3 and Example 10 the determination results of the continuity evaluation results of the first, second, and third connection structures are the same, but the connection resistance of Example 10 is higher than that of Example 3. The value of was low.
  • Example 5 and Example 12 the determination results of the continuity evaluation results of the first, second, and third connection structures are the same, but the value of connection resistance in Example 12 is greater than that in Example 5.
  • Example 7 and Example 14 the determination results of the continuity evaluation results of the first, second, and third connection structures are the same, but the value of connection resistance in Example 14 is greater than that in Example 7. Was low.

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