WO2024034386A1 - Particules électriquement conductrices, matériau électriquement conducteur et structure de connexion - Google Patents

Particules électriquement conductrices, matériau électriquement conducteur et structure de connexion Download PDF

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Publication number
WO2024034386A1
WO2024034386A1 PCT/JP2023/027151 JP2023027151W WO2024034386A1 WO 2024034386 A1 WO2024034386 A1 WO 2024034386A1 JP 2023027151 W JP2023027151 W JP 2023027151W WO 2024034386 A1 WO2024034386 A1 WO 2024034386A1
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conductive layer
conductive
tin
particles
conductive particles
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PCT/JP2023/027151
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English (en)
Japanese (ja)
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翔大 白石
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積水化学工業株式会社
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Priority to JP2023551188A priority Critical patent/JP7530523B2/ja
Publication of WO2024034386A1 publication Critical patent/WO2024034386A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • 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 conductive particles having a base particle and a conductive layer disposed on the surface of the base particle.
  • the present invention also relates to a conductive material and a connected structure using the conductive particles described above.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder resin. Further, as the conductive particles, conductive particles having a base particle and a conductive portion disposed on the surface of the base particle may be used.
  • the above-mentioned anisotropic conductive material is used to obtain various connected structures. Connections using the above-mentioned anisotropic conductive material include connections between flexible printed circuit boards and glass substrates (FOG (Film on Glass)), connections between semiconductor chips and flexible printed circuit boards (COF (Chip on Film)), and semiconductor chips. Examples include connection between a flexible printed circuit board and a glass substrate (COG (Chip on Glass)), and connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)).
  • Patent Document 1 discloses conductive particles comprising base particles and a conductive layer disposed on the surface of the base particles and containing nickel.
  • the conductive layer containing nickel has a melting point of 300° C. or higher.
  • the conductive layer containing nickel is an alloy layer containing nickel and tin, and the average content of tin is 5% by weight or more, based on 100% by weight of the entire conductive layer containing nickel. % by weight or less.
  • Patent Document 2 includes a base material particle and a conductive layer disposed on the surface of the base material particle and containing nickel, and the conductive layer containing nickel is composed of nickel, tin, and indium.
  • Conductive particles are disclosed which are alloy layers containing at least one of the following. In the conductive particles, the total average content of tin and indium is less than 5% by weight in 100% by weight of the region from the outer surface of the nickel-containing conductive layer to 1/2 the thickness inward. .
  • wearable displays In recent years, conductive materials used in wearable displays such as smart watches and smart glasses and various sensors have been attracting attention. Wearable displays are expected to be used continuously for long periods of time in various environments, so the conductive particles and connection structures used in wearable displays must be exposed to high temperature, high humidity, and high voltage for long periods of time. Performance that can withstand even the most extreme conditions is required.
  • connection resistance tends to increase when conductive particles that have been exposed to high temperatures are used, or when a connected structure using conductive particles is exposed to high temperatures.
  • An object of the present invention is to reduce the connection resistance when electrically connecting electrodes, and to maintain the Ni-Sn conductive layer even when exposed to high voltage in a high temperature and high humidity environment for a long time.
  • An object of the present invention is to provide conductive particles that can prevent charge transfer.
  • Another object of the present invention is to provide a conductive material and a connected structure using the above-mentioned conductive particles.
  • the present invention comprises base particles and a Ni--Sn conductive layer containing nickel and tin, and the Ni--Sn conductive layer is disposed on the surface of the base particles,
  • the average tin content in the entire area of the Ni-Sn conductive layer is less than 5% by weight, and when the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, the Ni -Sn Conductive particles are provided in which the maximum tin content is 5% by weight or more in the outer half-thickness region of the conductive layer.
  • the outer thickness of the Ni-Sn conductive layer is 1/ In the area No. 2, 80% by weight or more of tin is contained out of the total 100% by weight of tin contained in the entire Ni--Sn conductive layer.
  • the thickness of the Ni-Sn conductive layer is 15% or more. In the region, tin is included.
  • the thickness of the Ni-Sn conductive layer is 10% or more and In the region of less than 50%, tin is included in a content of 5% by weight or more.
  • the thickness of the Ni-Sn conductive layer is 10% or more and In the region of less than 50%, tin is contained in a content of 5% by weight or more, and in the region of 1/2 the outer thickness of the Ni-Sn conductive layer, the maximum value of the tin content is 5% by weight. % or more and 40% by weight or less.
  • the thickness of the Ni-Sn conductive layer is 30% or less. In the region, tin is contained in a content of 5% by weight or more.
  • the outer thickness of the Ni-Sn conductive layer is 1/ In region 2, the maximum tin content is 10% by weight or more.
  • the thickness of the Ni-Sn conductive layer is 30% or less.
  • the area contains tin in a content of 5% by weight or more, and the maximum value of the tin content is 10% by weight or more in the area of 1/2 the thickness outside the Ni-Sn conductive layer. .
  • the conductive particles have a particle diameter of 0.1 ⁇ m or more and 1000 ⁇ m or less.
  • the conductive particle has a plurality of protrusions on the outer surface of the Ni—Sn conductive layer.
  • a conductive material that includes the above-described conductive particles and a binder resin.
  • a first connection target member having a first electrode on its surface
  • a second connection target member having a second electrode on its surface
  • the first connection target member and the a connecting portion connecting a second connection target member the connecting portion being formed of the above-mentioned conductive particles, or of a conductive material containing the conductive particles and a binder resin.
  • a connected structure is provided, wherein the first electrode and the second electrode are electrically connected by the conductive particles.
  • the conductive particles according to the present invention include base particles and a Ni—Sn conductive layer containing nickel and tin.
  • the Ni-Sn conductive layer is arranged on the surface of the base particle, and the average tin content in the entire area of the Ni-Sn conductive layer is 5% by weight. less than
  • the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, in the outer half-thickness region of the Ni-Sn conductive layer, The maximum value of tin content is 5% by weight or more.
  • connection resistance can be lowered, and high temperature Furthermore, even when exposed to high voltage for a long time in a high humidity environment, charge movement in the Ni--Sn conductive layer can be prevented.
  • FIG. 1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.
  • FIG. 4 is a schematic diagram for explaining each region of the Ni--Sn conductive layer in the conductive particles according to the first embodiment of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing a connected structure using conductive particles according to the first embodiment of the present invention.
  • conductive particles Conventionally, when a conductive layer contains nickel, nickel is easily corroded, so when nickel is deposited, the connection resistance between the electrodes tends to increase. Further, when conductive particles containing nickel in the conductive layer are exposed to high voltage in a high temperature and high humidity environment, metal corrosion may occur and charges in the conductive layer may move. As a result, a short circuit may occur or conduction reliability may deteriorate.
  • the present inventor has discovered that even if it contains nickel, it is possible to lower not only the initial connection resistance but also the connection resistance after being exposed to the presence of acid, and that it is conductive in high temperature and high humidity environments.
  • the inventors focused on the content and distribution of tin within the conductive layer.
  • the present inventors have found that the above problem can be solved by controlling the tin content in the entire conductive layer and modifying the distribution of tin in the conductive layer.
  • the conductive particles according to the present invention include base particles and a Ni--Sn conductive layer containing nickel and tin, and the Ni--Sn conductive layer is arranged on the surface of the base particles.
  • the average content of tin in the entire area of the Ni--Sn conductive layer is less than 5% by weight.
  • the maximum value of tin content is 5% by weight or more.
  • connection resistance when electrically connecting electrodes using the conductive particles according to the present invention. Furthermore, connection resistance after exposure to the presence of acid can be reduced. Furthermore, even if the conductive particles are exposed to high voltage (e.g. 15V) for a long time (e.g. 500 hours) in a high temperature (e.g. 85°C) and high humidity (e.g. 85% RH) environment, Ni- Transfer of charges in the Sn conductive layer can be prevented.
  • high voltage e.g. 15V
  • a long time e.g. 500 hours
  • high temperature e.g. 85°C
  • high humidity e.g. 85% RH
  • connection resistance when a connected structure is produced using conductive particles stored in a high temperature and high humidity environment for a long period of time, an increase in connection resistance can be suppressed.
  • the particle diameter of the conductive particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, when the conductive particles are used to connect the electrodes, the contact area between the conductive particles and the electrodes is sufficiently large;
  • agglomerated conductive particles are less likely to be formed when forming a conductive part.
  • the distance between the electrodes connected via the conductive particles does not become too large, and the conductive part becomes difficult to peel off from the surface of the base particle.
  • the particle diameter of the conductive particles mentioned above means the diameter when the conductive particles are true spherical, and when the conductive particles have a shape other than true spherical, it is assumed that the conductive particles are true spheres equivalent to the volume. means the diameter of
  • the particle diameter of the conductive particles is preferably an average particle diameter, and preferably a number average particle diameter.
  • the particle diameter of the above-mentioned conductive particles can be determined, for example, by observing 50 arbitrary conductive particles with an electron microscope or optical microscope and calculating the average value of the particle diameter of each conductive particle, or by using a particle size distribution measuring device. It can be found using In observation using an electron microscope or an optical microscope, the particle diameter of each conductive particle is determined as the particle diameter in equivalent circle diameter. In observation using an electron microscope or an optical microscope, the average particle diameter of any 50 conductive particles in equivalent circle diameter is approximately equal to the average particle diameter in equivalent sphere diameter. In the particle size distribution measuring device, the particle diameter of each conductive particle is determined as the particle diameter in equivalent sphere diameter.
  • the average particle diameter of the conductive particles is preferably calculated using a particle size distribution measuring device.
  • the coefficient of variation (CV value) of the particle diameter of the conductive particles is preferably 10% or less, more preferably 5% or less.
  • the lower limit of the coefficient of variation of the particle diameter of the conductive particles is not particularly limited.
  • the coefficient of variation of the particle diameter of the conductive particles may be 0%, 0% or more, or 5% or more.
  • CV value The above coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ /Dn) x 100 ⁇ : Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameter of conductive particles
  • the shape of the conductive particles is not particularly limited.
  • the conductive particles may have a spherical shape, a shape other than a spherical shape, a flat shape, or the like.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • the conductive particles 1 shown in FIG. 1 have base particles 2 and a Ni—Sn conductive layer 3.
  • Ni—Sn conductive layer 3 contains nickel and tin.
  • the Ni—Sn conductive layer 3 is arranged on the surface of the base particle 2. In the first embodiment, the Ni—Sn conductive layer 3 is in contact with the surface of the base particle 2.
  • the conductive particles 1 are coated particles in which the surface of a base particle 2 is coated with a Ni—Sn conductive layer 3.
  • the Ni—Sn conductive layer 3 is a single-layer conductive layer.
  • the Ni-Sn conductive layer may cover the entire surface of the base particle, or the Ni-Sn conductive layer may cover a part of the surface of the base particle.
  • the conductive particles may have a conductive layer other than the Ni--Sn conductive layer.
  • the conductive particles may have multiple conductive layers.
  • the conductive particles 1 do not have a core substance, unlike the conductive particles 11 and 21 described below.
  • the conductive particles 1 do not have protrusions on the surface.
  • the conductive particles 1 are spherical.
  • the Ni--Sn conductive layer 3 has no protrusions on its outer surface. In this way, the conductive particles according to the present invention do not need to have protrusions on the surface of the Ni--Sn conductive layer, and may be spherical.
  • the conductive particles 1 do not have an insulating substance, unlike conductive particles 11 and 21 described later. However, the conductive particles 1 may have an insulating substance disposed on the outer surface of the Ni--Sn conductive layer 3.
  • the average content of tin in the entire area of the Ni--Sn conductive layer 3 is less than 5% by weight.
  • the tin content in the thickness direction of the Ni-Sn conductive layer 3 is measured by TEM-EDX, it is found that the tin content is found in the outer half-thickness region of the Ni-Sn conductive layer 3.
  • the maximum amount is 5% by weight or more.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • the conductive particles 11 shown in FIG. 2 include a base particle 2, a Ni—Sn conductive layer 12, a plurality of core substances 13, and a plurality of insulating substances 14.
  • the Ni—Sn conductive layer 12 is arranged on the surface of the base particle 2 so as to be in contact with the base particle 2.
  • the Ni—Sn conductive layer 12 is a single-layer conductive layer.
  • the Ni-Sn conductive layer may cover the entire surface of the base particle, or the Ni-Sn conductive layer may cover a part of the surface of the base particle.
  • the conductive particles may have a conductive layer other than the Ni--Sn conductive layer.
  • the conductive particles may have multiple conductive layers.
  • the conductive particles 11 have a plurality of protrusions 11a on the surface.
  • the Ni--Sn conductive layer 12 has a plurality of protrusions 12a on its outer surface.
  • a plurality of core substances 13 are arranged on the surface of the base particle 2.
  • a plurality of core materials 13 are embedded within the Ni--Sn conductive layer 12.
  • the core material 13 is arranged inside the protrusions 11a, 12a.
  • a Ni--Sn conductive layer 12 covers a plurality of core materials 13.
  • the outer surface of the Ni--Sn conductive layer 12 is raised by a plurality of core materials 13, and protrusions 11a and 12a are formed.
  • the conductive particles 11 have an insulating material 14 disposed on the outer surface of the Ni--Sn conductive layer 12. At least a portion of the outer surface of the Ni--Sn conductive layer 12 is covered with an insulating material 14.
  • the insulating substance 14 is made of an insulating material and is an insulating particle.
  • the conductive particles according to the present invention may have an insulating material disposed on the outer surface of the Ni--Sn conductive layer.
  • the conductive particles according to the present invention do not necessarily have to contain an insulating substance.
  • the average content of tin in the entire area of the Ni--Sn conductive layer 12 is less than 5% by weight.
  • the tin content in the thickness direction of the Ni-Sn conductive layer 12 is measured by TEM-EDX, it is found that the tin content in the outer half-thickness region of the Ni-Sn conductive layer 12 is The maximum amount is 5% by weight or more.
  • FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
  • the conductive particles 21 shown in FIG. 3 include a base particle 2, a Ni--Sn conductive layer 22A (first conductive layer), a plurality of core substances 13, and a plurality of insulating substances 14.
  • the conductive particles 21 have a Ni--Sn conductive layer 22A (first conductive layer) on the side opposite to the base particle 2 side, and a second conductive layer 22B on the base particle 2 side.
  • the only difference between the conductive particles 11 and the conductive particles 21 is the second conductive layer 22B. That is, in the conductive particles 11, a conductive layer having a single layer structure is formed, whereas in the conductive particles 21, a conductive layer having a two layer structure is formed. In the conductive particles 11, a Ni--Sn conductive layer 12 is formed, whereas in the conductive particles 21, a Ni--Sn conductive layer 22A (first conductive layer) and a second conductive layer 22B are formed. ing. In the conductive particles 21, a Ni--Sn conductive layer 22A (first conductive layer) and a second conductive layer 22B are formed as separate conductive layers.
  • the second conductive layer 22B is arranged on the surface of the base particle 2.
  • a second conductive layer 22B is arranged between the base material particles 2 and the Ni--Sn conductive layer 22A (first conductive layer).
  • the second conductive layer 22B is in contact with the base particle 2.
  • the Ni--Sn conductive layer 22A (first conductive layer) is in contact with the second conductive layer 22B. Therefore, the second conductive layer 22B is disposed on the surface of the base particle 2, and the Ni--Sn conductive layer 22A (first conductive layer) is disposed on the surface of the second conductive layer 22B.
  • the conductive particles 21 have a plurality of protrusions 21a on their surfaces.
  • the Ni--Sn conductive layer 22A (first conductive layer) has a plurality of protrusions 22Aa on its outer surface.
  • the second conductive layer 22B has a plurality of protrusions 22Ba on its outer surface.
  • the average tin content in the entire area of the Ni--Sn conductive layer 22A is less than 5% by weight.
  • the tin content in the thickness direction of the Ni-Sn conductive layer 22A is measured by TEM-EDX, it is found that the tin content is found in the outer half-thickness region of the Ni-Sn conductive layer 22A.
  • the maximum amount is 5% by weight or more.
  • the material of the base particles is not particularly limited.
  • the material of the base particles may be an organic material or an inorganic material.
  • Examples of the base material particles formed only from the above-mentioned organic material include resin particles.
  • Examples of the base material particles formed only from the above-mentioned inorganic material include inorganic particles excluding metals.
  • Examples of the base particles formed of both the organic material and the inorganic material include organic-inorganic hybrid particles. From the viewpoint of further improving the compression characteristics of the base particles, the base particles are preferably resin particles or organic-inorganic hybrid particles, and more preferably resin particles.
  • the organic materials mentioned above 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, and melamine.
  • 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, and melamine.
  • Formaldehyde resin benzoguanamine formaldehyde resin, urea formaldehyde resin, phenolic resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, Examples include polyetheretherketone, polyethersulfone, and divinylbenzene polymer.
  • the divinylbenzene polymer may be a divinylbenzene copolymer.
  • the divinylbenzene copolymer and the like examples include divinylbenzene-styrene copolymer and divinylbenzene-(meth)acrylic acid ester copolymer. Since the compression properties of the base particles can be easily controlled within a suitable range, the material of the base particles is a polymer obtained by polymerizing one or more polymerizable monomers having ethylenically unsaturated groups. It is preferable that
  • the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. Examples include monomers with different characteristics.
  • non-crosslinking monomer examples include vinyl compounds such as styrene monomers such as styrene, ⁇ -methylstyrene, and chlorostyrene; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acetate, vinyl butyrate, Acid vinyl ester compounds such as vinyl laurate and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; (meth)acrylic compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; ) acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc
  • meth)acrylate compounds oxygen atom-containing (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, glycidyl (meth)acrylate; (meth)acrylonitrile, etc.
  • oxygen atom-containing (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, glycidyl (meth)acrylate; (meth)acrylonitrile, etc.
  • Nitrile-containing monomers such as halogen-containing (meth)acrylate compounds such as trifluoromethyl (meth)acrylate and pentafluoroethyl (meth)acrylate; ⁇ -olefin compounds such as olefins such as diisobutylene, isobutylene, linear alene, ethylene, and propylene Compound: Examples of conjugated diene compounds include isoprene and butadiene.
  • crosslinking monomer examples include vinyl monomers such as divinylbenzene, 1,4-divinyloxybutane, and divinylsulfone as vinyl compounds; tetramethylolmethanetetra(meth)acrylate as (meth)acrylic compounds; , polytetramethylene glycol diacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,4-butan
  • the above-mentioned base material particles can be obtained by polymerizing the above-mentioned polymerizable monomer having an ethylenically unsaturated group.
  • the above polymerization method is not particularly limited, and includes known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, condensation polymerization), addition condensation, living polymerization, and living radical polymerization.
  • Other polymerization methods include suspension polymerization in the presence of a radical polymerization initiator.
  • examples of the inorganic materials include silica, alumina, barium titanate, zirconia, carbon black, silicate glass, borosilicate glass, lead glass, soda-lime glass, and alumina-silicate glass.
  • the base particles may be organic-inorganic hybrid particles.
  • the base particles may be core-shell particles.
  • examples of the inorganic material of the base particles include silica, alumina, barium titanate, zirconia, and carbon black.
  • the inorganic substance is not a metal.
  • the base particles formed from the silica are not particularly limited, but after hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, baking may be performed as necessary. Examples include base material particles obtained by carrying out this method.
  • Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed from a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core.
  • the core is an organic core.
  • the shell is an inorganic shell.
  • the base particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.
  • Examples of the material for the organic core include the organic materials described above.
  • the material for the inorganic shell examples include the inorganic substances listed as the material for the base particles described above.
  • the material of the inorganic shell is preferably silica.
  • the inorganic shell is preferably formed by forming a metal alkoxide into a shell-like material by a sol-gel method on the surface of the core, and then firing the shell-like material.
  • the metal alkoxide is a silane alkoxide.
  • the inorganic shell is preferably formed of silane alkoxide.
  • the particle diameter of the base particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more.
  • the particle size of the base particles is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, even more preferably 100 ⁇ m or less, particularly preferably 30 ⁇ m or less, and most preferably 10 ⁇ m or less.
  • the particle size of the base material particles is equal to or larger than the lower limit, the contact area between the conductive particles and the electrodes becomes large, which increases the reliability of conduction between the electrodes, and the connection between the conductive particles through the conductive particles increases. The connection resistance between the electrodes can be further reduced.
  • the particle diameter of the base particles is below the above upper limit, the conductive particles are easily compressed, and the connection resistance between the electrodes can be further lowered, and the distance between the electrodes can be further reduced. can.
  • the particle diameter of the base material particle mentioned above indicates the diameter when the base material particle is true spherical, and when the base material particle has a shape other than true spherical shape, it is assumed that the base material particle is a true sphere equivalent to the volume. means the diameter of
  • the particle diameter of the above-mentioned base material particles indicates the number average particle diameter.
  • the particle diameter of the above-mentioned base material particles can be determined by observing 50 arbitrary base material particles with an electron microscope or optical microscope and calculating the average value of the particle diameter of each base material particle, or by using a particle size distribution measuring device. Desired. In observation using an electron microscope or an optical microscope, the particle diameter of each base particle is determined as the particle diameter in equivalent circle diameter. In observation using an electron microscope or an optical microscope, the average particle diameter of any 50 base particles in equivalent circle diameter is approximately equal to the average particle diameter in equivalent sphere diameter. In the particle size distribution measuring device, the particle diameter of each base material particle is determined as the particle diameter in equivalent sphere diameter.
  • the average particle diameter of the base particles is preferably calculated using a particle size distribution measuring device.
  • the particle diameter of the base particle in the conductive particles for example, it can be measured as follows.
  • a conductive particle content of 30% by weight is added to "Technovit 4000" manufactured by Kulzer and dispersed to prepare an embedded resin body for conductive particle inspection.
  • IM4000 manufactured by Hitachi High-Technologies
  • a cross section of the conductive particles is cut out so as to pass through the center of the base particle of the conductive particles dispersed in the embedded resin body for inspection.
  • FE-SEM field emission scanning electron microscope
  • the image magnification was set to 25,000 times, 50 conductive particles were randomly selected, and the base material particles of each conductive particle were observed. do.
  • the particle diameter of the base material particle in each conductive particle is measured, and the arithmetic average of the measurements is taken as the particle diameter of the base material particle.
  • the conductive particles include a Ni--Sn conductive layer containing nickel and tin.
  • the average tin content in the entire area of the Ni--Sn conductive layer is less than 5% by weight.
  • the conductive particles when the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, in the outer half-thickness region (R1) of the Ni-Sn conductive layer, The maximum value of tin content is 5% by weight or more.
  • the region R1 is a region having a thickness of 50% outside the Ni--Sn conductive layer.
  • FIG. 4 is a schematic diagram for explaining each region of the Ni—Sn conductive layer in the conductive particles according to the first embodiment of the present invention.
  • FIG. 4 is a schematic diagram for explaining each region of the Ni—Sn conductive layer 3 in the conductive particle 1. As shown in FIG.
  • the outer 1/2 thickness region (R1) of the Ni-Sn conductive layer is a region extending from the outer surface of the Ni-Sn conductive layer inward to 1/2 the thickness of the Ni-Sn conductive layer. .
  • the region R1 is the region outside the broken line L1 of the Ni—Sn conductive layer 3 in FIG.
  • the region R1 is the outer surface portion of the Ni—Sn conductive layer 3.
  • the region R1 is a region different from the region of the Ni—Sn conductive layer 3 on the base particle 2 side.
  • the inner 1/2 thickness region (R2) of the Ni-Sn conductive layer is a region extending from the inner surface of the Ni-Sn conductive layer toward the outside to 1/2 the thickness of the Ni-Sn conductive layer. .
  • the region R2 is a region inside the broken line L1 of the Ni--Sn conductive layer 3 in FIG.
  • the region R2 is a region of the Ni—Sn conductive layer 3 on the base particle 2 side.
  • the region R2 is a region different from the outer surface portion of the Ni—Sn conductive layer 3.
  • the average content of tin in the entire area of the Ni—Sn conductive layer is less than 5% by weight. Since the conductive particles have the above configuration, the initial resistance can be lowered. From the viewpoint of further lowering the initial resistance, the average tin content in the entire area of the Ni-Sn conductive layer is preferably 4.5% by weight or less, more preferably 4.0% by weight or less, and even more preferably is 3.5% by weight or less. From the viewpoint of further lowering the connection resistance after being exposed to the presence of an acid, the average content of tin in the entire area of the Ni--Sn conductive layer exceeds 0% by weight, preferably 0.1% by weight. It is at least 0.5% by weight, more preferably at least 0.5% by weight.
  • the Ni—Sn layer preferably contains nickel as a main metal.
  • the average content of nickel in the entire area of the Ni--Sn conductive layer is preferably 50% by weight or more, more preferably 80% by weight or more, and preferably 99.9% by weight or less, more preferably 99.5% by weight. % by weight or less.
  • the average content of nickel and tin in the entire area of the Ni--Sn conductive layer can be measured by ICP-MS method or the like.
  • the conductive particles when the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, in the outer half-thickness region (R1) of the Ni-Sn conductive layer, The maximum value of tin content is 5% by weight or more. Since the conductive particles have the above-described structure, it is possible to prevent charge movement in the Ni--Sn conductive layer even when exposed to high voltage for a long time in a high temperature and high humidity environment.
  • the maximum value of the tin content of the Ni-Sn conductive layer is in the region R1.
  • the maximum tin content in the entire region of the Ni—Sn conductive layer exists in the region R1.
  • the region where the tin content has the maximum value in the entire region of the Ni—Sn conductive layer is the region R1.
  • the tin content preferably reaches a maximum value in the region R1.
  • the maximum tin content in the region R1 is the tin content in the region R2.
  • the amount is greater than the maximum value.
  • the maximum value of the tin content in the Ni-Sn conductive layer is in the region R1. The maximum tin content is preferred.
  • tin is unevenly distributed in the thickness direction of the Ni--Sn conductive layer. In the conductive particles, tin is unevenly distributed in the thickness direction of the Ni--Sn conductive layer.
  • the conductive particles preferably have different tin contents such that the tin content in the region R1 is higher than the tin content in the region R2 in the Ni—Sn conductive layer. It is preferable that the content has a gradient. In the Ni--Sn conductive layer, it is preferable that tin is unevenly distributed so that it is present more in the region R1 than in the region R2. In the Ni—Sn conductive layer, the average tin content in the region R1 is preferably larger than the average tin content in the region R2. The presence of such a concentration difference and concentration gradient can further reduce the connection resistance after exposure to the presence of acid, and the conductive particles can be exposed to high voltage for a long time in a hot and humid environment. Even if exposed to the Ni--Sn conductive layer, movement of charges in the Ni--Sn conductive layer can be more effectively prevented.
  • the average content of tin in the region R1 is preferably 0.5% by weight or more, more preferably 1% by weight, based on 100% by weight of the entire region R1.
  • the content is at least .0% by weight, more preferably at least 3.0% by weight, preferably at most 10% by weight, more preferably at most 9.0% by weight, even more preferably at most 8.0% by weight.
  • the average content of tin in the region R2 is preferably 10% by weight or less, more preferably 5% by weight, based on the entire 100% by weight of the region R2.
  • the content is preferably 3% by weight or less.
  • the lower limit of the average content of tin in the region R2 in 100% by weight of the entire region R2 is not particularly limited.
  • the average content of tin in the region R2 may be 3% by weight or more out of 100% by weight of the entire region R2.
  • the conductive particles according to the present invention it is very important to control the distribution of tin contained in the Ni--Sn conductive layer in the thickness direction.
  • the content of tin in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, the content of tin in the region R1 is out of the total 100% by weight of tin contained in the entire Ni-Sn conductive layer.
  • the amount is preferably 65% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more.
  • the 1/2 region (R1) contains 80% by weight or more of tin out of the total 100% by weight of tin contained in the entire Ni--Sn conductive layer.
  • the content of tin in the region R1 is more preferably 85% by weight or more, even more preferably 90% by weight or more, particularly preferably 95% by weight or more, out of the total 100% by weight of tin contained in the entire Ni--Sn conductive layer. % by weight or more, most preferably 100% by weight (total amount).
  • the content of tin in the region R1 is equal to or higher than the lower limit of the total 100% by weight of tin contained in the entire Ni-Sn conductive layer, the connection resistance after being exposed to the presence of an acid will be increased. Even if the conductive particles are exposed to high voltage for a long time in a high temperature and high humidity environment, the transfer of charges in the Ni--Sn conductive layer can be even more effectively prevented.
  • the proportion of the area containing tin in 100% of the thickness of the Ni--Sn conductive layer is preferably 5% or more, more preferably is 15% or more, preferably 95% or less, more preferably 80% or less, even more preferably 50% or less.
  • the Ni-Sn when the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, the Ni-Sn Preferably, tin is contained in a region where the conductive layer has a thickness of 15% or more.
  • the proportion of the area containing tin in 100% of the thickness of the conductive layer is about 10%.
  • the proportion of the area containing tin in 100% of the thickness of the Ni-Sn conductive layer is equal to or more than the above-mentioned lower limit and below the above-mentioned upper limit, the connection after being exposed to the presence of acid is The resistance can be lowered even further, and even if the conductive particles are exposed to high voltage for a long time in a high temperature and high humidity environment, the transfer of charge in the Ni-Sn conductive layer can be more effectively prevented. can.
  • the thickness of the area containing tin peak width in the distribution curve
  • the area It is very important to control the relationship between the maximum value of tin content (peak height in the distribution curve) and the maximum tin content (peak height in the distribution curve). That is, in the conductive particles, in the tin content distribution curve measured by TEM-EDX, the distance in the thickness direction from the outer surface when the horizontal axis is the thickness of the Ni-Sn conductive layer as 100% ( %) and the vertical axis is the tin content (weight %), it is very important to control the peak width and peak height of the distribution curve.
  • the shape of the tin content distribution curve may be a mountain shape or a portion of a mountain shape.
  • the tin content distribution curve may be unimodal or multimodal.
  • the tin content distribution curve may have one peak or a plurality of peaks.
  • the proportion of the area containing tin in 100% of the thickness of the Ni--Sn conductive layer is the sum of the widths of each peak.
  • the distribution curve of the tin content preferably has one peak, and as described above, the peak (the maximum value of the tin content of the Ni--Sn conductive layer) is present in the region R1. It is preferred that the Ni--Sn conductive layer be present on the outermost surface of the Ni--Sn conductive layer.
  • the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, it is found that tin is distributed over a wide area in the thickness direction of the Ni-Sn conductive layer, and The maximum value of the tin content in the Ni--Sn conductive layer may be small.
  • the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX, it is found that tin is distributed over a wide area in the thickness direction of the Ni-Sn conductive layer, and In the outer half-thickness region (R1) of the Ni—Sn conductive layer, the maximum value of the tin content may be small.
  • the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX
  • tin is distributed in a narrow region in the thickness direction of the Ni-Sn conductive layer
  • the maximum value of the tin content may be large.
  • the tin content in the thickness direction of the Ni-Sn conductive layer is measured by TEM-EDX
  • tin is distributed in a narrow region in the thickness direction of the Ni-Sn conductive layer, and In the outer half-thickness region (R1) of the Ni—Sn conductive layer, the maximum value of the tin content may be large.
  • the proportion of the area containing tin in the 100% thickness of the Ni--Sn conductive layer is particularly preferably 20% or more, most preferably 25% or more. Further, in the above case, the proportion of the area containing tin in the 100% thickness of the Ni--Sn conductive layer is particularly preferably 50% or less, most preferably 40% or less. In the above case, the tin content in the thickness direction of the Ni--Sn conductive layer is measured by TEM-EDX.
  • tin is contained in a content of 5% by weight or more in a region where the thickness of the Ni--Sn conductive layer is 10% or more and less than 50%.
  • the area where the tin content is 5% by weight or more is preferably 8% or more, more preferably 10% or more, and even more preferably 12.5% of the 100% thickness of the Ni-Sn conductive layer. % or more, preferably less than 50%, more preferably 40% or less, even more preferably 30% or less.
  • the tin content in the thickness direction of the Ni--Sn conductive layer is measured by TEM-EDX.
  • the maximum tin content in the outer 1/2 thickness region (R1) of the Ni-Sn conductive layer is 5% by weight or more, preferably 7% by weight or more, more preferably 10% by weight. % or more, preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, particularly preferably 20% by weight or less.
  • tin is contained at a content of 5% by weight or more in a region where the thickness of the Ni-Sn conductive layer is 10% or more and less than 50%, and the thickness of the Ni-Sn conductive layer is In the outer half-thickness region (R1), the maximum tin content is more preferably 5% by weight or more and 40% by weight or less.
  • the proportion of the area containing tin in the 100% thickness of the Ni--Sn conductive layer is particularly preferably 5% or more, most preferably 10% or more.
  • the proportion of the area containing tin in the 100% thickness of the Ni--Sn conductive layer is more preferably 40% or less, particularly preferably 30% or less, and most preferably 25% or less.
  • the tin content in the thickness direction of the Ni--Sn conductive layer is measured by TEM-EDX.
  • tin is contained in a content of 5% by weight or more in a region where the thickness of the Ni--Sn conductive layer is 30% or less.
  • the area where the tin content is 5% by weight or more is preferably 0.1% or more, more preferably 0.5% or more, and even more preferably is 1.0% or more, preferably 30% or less, more preferably 25% or less, even more preferably 20% or less, and most preferably 10% or less.
  • the tin content in the thickness direction of the Ni--Sn conductive layer is measured by TEM-EDX.
  • the maximum tin content in the outer 1/2 thickness region (R1) of the Ni-Sn conductive layer is 5% by weight or more, preferably 10% by weight or more, and more preferably 15% by weight. % or more.
  • the maximum value of the tin content is preferably 95% by weight or less, more preferably 90% by weight or less, It is more preferably 80% by weight or less, particularly preferably 50% by weight or less, most preferably 40% by weight or less.
  • the tin content is 5% by weight or more in the area where the thickness of the Ni-Sn conductive layer is 30% or less, and the tin content is 5% by weight or more in the area where the thickness of the Ni-Sn conductive layer is 1/2 In region (R1), the maximum tin content is more preferably 10% by weight or more.
  • the average content of nickel and tin in the region R1, the average content of nickel and tin in the region R2, the maximum value of the tin content in the region R1, and the maximum value of the tin content in the region R2 are as follows: It can be measured by TEM-EDX. Specifically, a thin film section of the conductive particles is produced using a focused ion beam. Next, using a transmission electron microscope FE-TEM ("JEM-2010FEF" manufactured by JEOL Ltd.) and an energy dispersive X-ray spectrometer (EDS), each of nickel and tin was measured in the thickness direction of the Ni-Sn conductive layer. Measure the content.
  • the outermost inflection point on the curve showing the content of all metals contained in the Ni-Sn conductive layer is The starting point (thickness 0%) is taken as the innermost inflection point and the end point (thickness 100%) in the thickness direction of the Ni--Sn conductive layer.
  • the Ni—Sn conductive layer may contain nickel, tin, and a metal other than nickel and tin.
  • Metals other than nickel and tin include silver, copper, platinum, zinc, iron, lead, aluminum, cobalt, indium, palladium, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, tungsten, molybdenum, and Examples include tin-doped indium oxide (ITO). These metals may be used alone or in combination of two or more.
  • the average content of metals other than nickel and tin in the entire area of the Ni--Sn conductive layer is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less.
  • the lower limit of the average content of metals other than nickel and tin in the entire area of the Ni--Sn conductive layer is not particularly limited.
  • the average content of the metal other than nickel and tin in the entire area of the Ni--Sn conductive layer may be 0.01% by weight or more, or 0.1% by weight or more.
  • the Ni-Sn conductive layer contains a metal other than the nickel and tin
  • the average nickel content and the average tin content in the region R1 and the region R2 are the same as the nickel content and the tin content.
  • the total amount including the content is calculated as 100% by weight.
  • the thickness of the Ni--Sn conductive layer is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 80 nm or more, and preferably 500 nm or less, more preferably 300 nm or less.
  • the thickness of the Ni--Sn conductive layer mentioned above indicates the average thickness of the Ni--Sn conductive layer in the conductive particles.
  • the method for forming the Ni--Sn conductive layer is not particularly limited.
  • Methods for forming the Ni-Sn conductive layer include, for example, electroless plating, electroplating, physical vapor deposition, and coating the surfaces of particles with metal powder or a paste containing metal powder and a binder. Examples include a method to do so. Among these, a method using electroless plating is preferred because the formation of the Ni--Sn conductive layer is simple.
  • Examples of the physical vapor deposition method include vacuum vapor deposition, ion plating, and ion sputtering.
  • Methods for controlling the content and distribution of nickel and tin in the Ni-Sn conductive layer include, for example, a method of adjusting the concentration of tin and a complexing agent in the plating solution in electroless plating, and a method of controlling the concentration of tin and complexing agent in the plating solution, and Examples include a method of adjusting pH.
  • the above-mentioned conductive particles may include multiple conductive layers.
  • the conductive particles may include a conductive layer (another conductive layer) other than the Ni—Sn conductive layer.
  • the Ni—Sn conductive layer is preferably the outermost layer of the conductive particles.
  • the Ni—Sn conductive layer is preferably the outermost conductive layer.
  • the structure of the conductive layers other than the Ni--Sn conductive layer is not particularly limited.
  • the material of the conductive layers other than the Ni--Sn conductive layer may be the same as or different from the material of the Ni--Sn conductive layer.
  • the conductive particles according to the present invention preferably have protrusions on the surface.
  • the Ni--Sn conductive layer preferably has protrusions on its outer surface.
  • An oxide film is often formed on the surface of an electrode connected by conductive particles.
  • the conductive particles have an insulating substance on their surface, or when the conductive particles are dispersed in a resin and used as a conductive material, the protrusions of the conductive particles create a gap between the conductive particles and the electrode. Insulating materials or resins can be effectively eliminated. Therefore, the reliability of conduction between the electrodes can be improved.
  • the number of the protrusions is plural.
  • the number of protrusions on the outer surface of the conductive layer per conductive particle is preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of projections is not particularly limited.
  • the number of the protrusions is preferably 1000 or less, more preferably 800 or less.
  • the upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles, etc.
  • the average height of the plurality of protrusions is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, and more preferably 0.2 ⁇ m or less.
  • the average height of the protrusions can be calculated by the following method. Fifty conductive particles of the present invention are observed using an electron microscope or an optical microscope, and the heights of all the protrusions on the periphery of the observed conductive particles are measured. It is determined by measuring the height of the convex portion using a surface on which no protrusions are formed as a reference surface, and calculating the average value.
  • the surface area of the portion with the protrusions is preferably 10% or more, more preferably 20% of the total surface area of the outer surface of the Ni-Sn conductive layer. % or more, more preferably 30% or more.
  • the upper limit of the ratio of the surface area of the portion with the protrusions to 100% of the total surface area of the outer surface of the Ni--Sn conductive layer is not particularly limited, but is usually 100% or less, preferably 99% or less.
  • the ratio of the surface area of the portion where the protrusion is present can be calculated by the following method. It is determined by observing 50 conductive particles of the present invention with an electron microscope or an optical microscope, measuring the ratio of the areas of the portions appearing as protrusions in the orthogonal projection plane, and calculating the average value.
  • the core material Since the core material is embedded in the Ni--Sn conductive layer, it is easy to make the Ni--Sn conductive layer have a plurality of protrusions on its outer surface. However, in order to form protrusions on the outer surfaces of the conductive particles and the Ni--Sn conductive layer, it is not necessary to use a core material, and it is preferable not to use a core material.
  • the conductive particles do not have a core material inside and inside the Ni--Sn conductive layer for raising the outer surface of the Ni--Sn conductive part.
  • the Ni--Sn conductive layer does not include a core material inside and inside the Ni--Sn conductive layer for raising the outer surface of the Ni--Sn conductive layer.
  • the above protrusions can be formed by attaching a core substance to the surface of the base particle and then forming a Ni-Sn conductive layer by electroless plating, or by electroless plating the Ni-Sn conductive layer on the surface of the base particle.
  • Examples include a method of forming a Sn conductive layer, then depositing a core material, and further forming a Ni--Sn conductive layer by electroless plating.
  • Other methods for forming the protrusions include a method of adding a core material during the formation of the Ni--Sn conductive layer on the surface of the base material particles.
  • the core material is added to a dispersion of the base material particles, and the core material is applied to the surface of the base material particles by, for example, van der Waals force.
  • methods of accumulating and adhering the base particles, and methods of adding a core substance to a container containing the base particles and attaching the core substance to the surface of the base particles through mechanical action such as rotation of the container. a method of accumulating and depositing the core material on the surface of the base particles in the dispersion is preferred because it is easy to control the amount of the core material to be deposited.
  • Examples of the substance constituting the core substance include conductive substances and non-conductive substances.
  • Examples of the conductive substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers.
  • Examples of the conductive polymer include polyacetylene.
  • Examples of the non-conductive substance include silica, alumina, barium titanate, and zirconia. Among these, metal is preferred because it can improve conductivity and effectively lower connection resistance.
  • the core material is a metal particle.
  • Examples of the above metals include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, and tin-lead.
  • Examples include alloys composed of two or more metals, such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and tungsten carbide. Among them, nickel, copper, silver or gold is preferred.
  • the metal for forming the core material may be the same as or different from the metal for forming the conductive layer.
  • the metal for forming the core material preferably includes the metal for forming the conductive layer.
  • the metal for forming the core material preferably contains nickel.
  • the materials for the core substance include barium titanate (Mohs hardness 4.5), nickel (Mohs hardness 5), silica (silicon dioxide, Mohs hardness 6-7), titanium oxide (Mohs hardness 7), zirconia (Mohs hardness: 8 to 9), alumina (Mohs hardness: 9), tungsten carbide (Mohs hardness: 9), and diamond (Mohs hardness: 10).
  • the inorganic particles are preferably nickel, silica, titanium oxide, zirconia, alumina, tungsten carbide, or diamond, and more preferably silica, titanium oxide, zirconia, alumina, tungsten carbide, or diamond.
  • the inorganic particles are more preferably titanium oxide, zirconia, alumina, tungsten carbide, or diamond, and particularly preferably zirconia, alumina, tungsten carbide, or diamond.
  • the Mohs hardness of the material of the core substance is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, particularly preferably 7.5 or more.
  • the shape of the core material is not particularly limited.
  • the shape of the core material is preferably a block.
  • Examples of the core substance include particulate lumps, aggregates of a plurality of microparticles, and irregularly shaped lumps.
  • the average diameter (average particle diameter) of the core material is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, and more preferably 0.2 ⁇ m or less.
  • the average diameter of the core substance is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes is effectively reduced.
  • the "average diameter (average particle diameter)" of the above-mentioned core substance indicates the number average diameter (number average particle diameter).
  • the average diameter of the core substance can be determined, for example, by observing 50 arbitrary core substances with an electron microscope or an optical microscope and calculating the average value.
  • the conductive particles according to the present invention preferably include an insulating material disposed on the outer surface of the Ni--Sn conductive layer.
  • an insulating material disposed on the outer surface of the Ni--Sn conductive layer.
  • the insulating substance is preferably insulating particles, since the insulating substance can be more easily removed during crimping between the electrodes.
  • thermoplastic resin examples include vinyl polymers and vinyl copolymers.
  • thermosetting resin examples include epoxy resin, phenol resin, and melamine resin.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and methylcellulose.
  • the insulating resin preferably contains a water-soluble resin, and more preferably contains polyvinyl alcohol.
  • Examples of methods for disposing an insulating substance on the surface of the Ni—Sn conductive layer include chemical methods, physical or mechanical methods, and the like.
  • Examples of the chemical methods include interfacial polymerization, suspension polymerization in the presence of particles, and emulsion polymerization.
  • Examples of the physical or mechanical methods include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. Among these, a method in which the insulating substance is disposed on the surface of the conductive layer via a chemical bond is preferred because the insulating substance is difficult to detach.
  • the outer surface of the Ni—Sn conductive layer 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 layer and the surface of the insulating particles may not be directly chemically bonded to each other, but may be indirectly chemically bonded to each other through a compound having a reactive functional group.
  • the carboxyl group may be chemically bonded to a functional group on the surface of the insulating particle via a polymer electrolyte such as polyethyleneimine.
  • the average diameter (average particle diameter) of the above-mentioned insulating substance can be appropriately selected depending on the particle diameter of the conductive particles, the use of the conductive particles, etc.
  • the average diameter (average particle diameter) of the insulating substance is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 1 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
  • the average diameter of the insulating substance is equal to or larger than the above lower limit, when the conductive particles are dispersed in the binder resin, the conductive layers of the plurality of conductive particles are difficult to come into contact with each other.
  • the "average diameter (average particle diameter)" of the above-mentioned insulating substance indicates the number average diameter (number average particle diameter).
  • the average diameter of the insulating substance is determined using a particle size distribution measuring device or the like.
  • the electrically conductive material according to the present invention includes the above-mentioned electrically conductive particles and a binder resin.
  • the conductive particles are preferably used as a conductive material by being dispersed in a binder resin, and preferably used as a conductive material by being dispersed in a binder resin.
  • the conductive material is an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection between electrodes.
  • the conductive material is a circuit connection material.
  • the above binder resin is not particularly limited.
  • As the binder resin a known insulating resin is used.
  • binder resin examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. Only one type of the binder resin may be used, or two or more types may be used in combination.
  • the vinyl resin examples include vinyl acetate resin, acrylic resin, and styrene resin.
  • the thermoplastic resin examples include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins.
  • the curable resin examples include epoxy resin, urethane resin, polyimide resin, and unsaturated polyester resin. Note that the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The above-mentioned curable resin may be used in combination with a curing agent.
  • thermoplastic block copolymers examples include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated products of styrene-butadiene-styrene block copolymers, and styrene-isoprene block copolymers.
  • examples include hydrogenated products of styrene block copolymers.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the conductive materials include, for example, fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, heat stabilizers, and light stabilizers. It may contain various additives such as a UV absorber, a lubricant, an antistatic agent, and a flame retardant.
  • the conductive material according to the present invention can be used as a conductive paste, a conductive film, and the like.
  • the conductive material according to the present invention is a conductive film
  • a film not containing conductive particles may be laminated on a conductive film containing 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, even more preferably 50% by weight or more, particularly preferably 70% by weight or more, and preferably 99% by weight or more. It is 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 members connected by the conductive material becomes even higher.
  • 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 40% by weight or less, and more preferably 20% by weight or less. , more preferably 10% by weight or less.
  • the content of the conductive particles is at least the above lower limit and at most the above upper limit, the reliability of conduction between the electrodes becomes even higher.
  • connection structure can be obtained by connecting members to be connected using the conductive particles or using a conductive material containing the conductive particles and a binder resin.
  • the connection structure includes a first connection target member, a second connection target member, and a connection part connecting the first and second connection target members, and the connection part has the above-mentioned conductive property.
  • the connected structure be formed of particles or a conductive material containing the above-mentioned conductive particles and a binder resin.
  • the first electrode and the second electrode are electrically connected by the conductive particles described above. If conductive particles are used, the connection itself is the conductive particle. That is, the first and second connection target members are connected by the conductive particles.
  • FIG. 5 schematically shows a cross-sectional view of a connected structure using conductive particles according to the first embodiment of the present invention.
  • connection structure 51 shown in FIG. 5 connects a first connection target member 52, a second connection target member 53, and a connection part 54 connecting the first and second connection target members 52 and 53. Be prepared.
  • the connecting portion 54 is formed by curing a conductive material containing the conductive particles 1. Note that in FIG. 5, the conductive particles 1 are shown schematically for convenience of illustration. In place of the conductive particles 1, conductive particles 11, 21, etc. may be used.
  • the first connection target member 52 has a plurality of first electrodes 52a on its surface (upper surface).
  • the second connection target member 53 has a plurality of second electrodes 53a on the front surface (lower surface).
  • the first electrode 52a and the second electrode 53a are electrically connected by one or more conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
  • the method for manufacturing the above-mentioned connected structure is not particularly limited.
  • the conductive material is placed between a first member to be connected and a second member to be connected, a laminate is obtained, and then the laminate is heated and pressurized. Examples include methods.
  • the pressure of the above pressurization is about 9.8 ⁇ 10 4 Pa to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120°C to 220°C.
  • connection target members include electronic components such as semiconductor chips, electronic components such as capacitors and diodes, and circuit boards such as printed circuit boards, flexible printed circuit boards, glass epoxy boards, and glass substrates. It is preferable that the member to be connected is an electronic component.
  • the conductive particles are preferably used for electrical connection of electrodes in electronic components.
  • the electrodes provided on the connection target member include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, silver electrodes, molybdenum electrodes, and tungsten electrodes.
  • 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 said electrode when the said electrode is an aluminum electrode, it may be an electrode formed only with aluminum, and the electrode may be an electrode in which an aluminum layer is 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 elements include Sn, Al, and Ga.
  • Base particle A divinylbenzene copolymer resin particles with a particle size of 3.0 ⁇ m (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.)
  • Base material particle B Base material particle that differs from base material particle A only in particle size and has a particle size of 2.5 ⁇ m.
  • Base material particle C Only differs from base material particle A in particle size and has a particle size of 10.0 ⁇ m.
  • Base material particle D Core-shell type organic-inorganic hybrid particle with a particle diameter of 3.0 ⁇ m (produced according to Synthesis Example 1 below)
  • Base particle E organic-inorganic hybrid particle having a particle diameter of 3.0 ⁇ m (produced according to Synthesis Example 2 below)
  • the base material particles E were obtained by baking at 350° C. for 2 hours.
  • Example 1 After dispersing 10 parts by weight of the above base material particles A in 100 parts by weight of an alkaline solution containing 5% by weight of palladium catalyst liquid using an ultrasonic disperser, the base material particles A were taken out by filtering the solution. . Next, the base particles A were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surfaces of the base particles A. After thoroughly washing the surface-activated base material particles A with water, they were added to 500 parts by weight of distilled water and dispersed to obtain a suspension (0).
  • a nickel plating solution (1) (pH 8.5) containing 0.14 mol/L of nickel sulfate, 0.46 mol/L of dimethylamine borane, and 0.2 mol/L of sodium citrate was prepared. While stirring the suspension (0) at 60°C, the nickel plating solution (1) was gradually dropped into the suspension (0) to perform electroless nickel-boron alloy plating. 1) was obtained.
  • a nickel plating solution (2) (pH 8.0) containing 0.14 mol/L of nickel sulfate and 0.45 mol/L of hydrazine was prepared. While stirring the suspension (1) at 65°C, the nickel plating solution (2) was gradually dropped into the suspension (1) to perform electroless nickel plating, and the suspension (2) Obtained.
  • a nickel plating solution (3) (pH 8.0) containing 0.14 mol/L of nickel sulfate, 0.09 mol/L of sodium stannate trihydrate, and 0.45 mol/L of sodium gluconate was prepared. While stirring the suspension (2) at 65°C, the nickel plating solution (3) was gradually dropped into the suspension (2) to perform electroless nickel-tin alloy plating, and the suspension ( 3) was obtained.
  • the particles are taken out by filtering the suspension (3), washed with water, and dried to form conductive particles with a Ni-Sn conductive layer (thickness 136 nm) arranged on the surface of the base particle A. I got it.
  • Example 2 A nickel plating solution (pH 8.0) containing 0.07 mol/L of nickel sulfate, 0.045 mol/L of sodium stannate trihydrate, and 0.225 mol/L of sodium gluconate was prepared. Conductive particles were obtained in the same manner as in Example 1, except that this nickel plating solution was used instead of nickel plating solution (3).
  • Example 3 Conductive particles were obtained in the same manner as in Example 1, except that the nickel plating solution (2) and the nickel plating solution (3) were simultaneously dropped into the suspension (1).
  • Example 4 Conductive particles were deposited in the same manner as in Example 1, except that the nickel plating solution (1), the nickel plating solution (2), and the nickel plating solution (3) were simultaneously dropped into the suspension (0). I got it.
  • Example 5 The pH of the nickel plating solution (1), the nickel plating solution (2) was changed to 8.5, and the pH of the nickel plating solution (3) was changed to 8.5 to the suspension (0). Conductive particles were obtained in the same manner as in Example 1, except that a changed nickel plating solution was dropped at the same time.
  • Example 6 Conductive particles were obtained in the same manner as in Example 1, except that the dropping amounts of the nickel plating solution (1), the nickel plating solution (2), and the nickel plating solution (3) were increased by 1.3 times. .
  • Example 7 Conductive particles were obtained in the same manner as in Example 1, except that the dropping amounts of the nickel plating solution (1), the nickel plating solution (2), and the nickel plating solution (3) were increased by 0.8 times. .
  • Example 8 The concentration of sodium stannate trihydrate in the nickel plating solution (3) was changed from 0.09 mol/L to 0.15 mol/L, and the concentration of sodium gluconate was changed from 0.45 mol/L to 0.75 mol/L. A nickel plating solution changed to L was prepared. Conductive particles were obtained in the same manner as in Example 1, except that this nickel plating solution was used instead of nickel plating solution (3).
  • Example 9 The concentration of sodium stannate trihydrate in the nickel plating solution (3) was changed from 0.09 mol/L to 0.30 mol/L, and the concentration of sodium gluconate was changed from 0.45 mol/L to 0.90 mol/L.
  • a nickel plating solution was prepared using a modified nickel plating solution. Conductive particles were obtained in the same manner as in Example 1, except that this nickel plating solution was used instead of nickel plating solution (3).
  • Example 10 2 g of Ni particle slurry (average particle diameter: 150 nm) was added to the above suspension (0) over 3 minutes to obtain a suspension containing base particles to which the core material was attached.
  • Conductive particles were obtained in the same manner as in Example 1, except that the obtained suspension was used. Protrusions were formed on the outer surface of the Ni--Sn conductive layer of the obtained conductive particles.
  • Example 11 0.5 g of alumina particle slurry (average particle diameter: 150 nm) was added to the suspension (0) over 3 minutes to obtain a suspension containing base particles to which the core material was attached. Conductive particles were obtained in the same manner as in Example 1, except that the obtained suspension was used. Protrusions were formed on the outer surface of the Ni--Sn conductive layer of the obtained conductive particles.
  • Example 12 Protrusions were formed in the above suspension (0) without using Ni particle slurry by adjusting the amount of precipitation to be partially changed during formation of the conductive part, and protrusions were formed on the outer surface of the Ni-Sn conductive layer. Conductive particles were obtained in the same manner as in Example 1, except that .
  • Example 13 to 16 Conductive particles were obtained in the same manner as in Example 10, except that the base particles were changed as shown in Table 3 below. Protrusions were formed on the outer surface of the Ni--Sn conductive layer of the obtained conductive particles.
  • Example 17 (1) Preparation of insulating particles A 1000 mL separable flask equipped with a four-necked separable cover, a stirring blade, a three-way cock, a cooling tube, and a temperature probe was prepared. Into the separable flask, 100 mmol of methyl methacrylate, 1 mmol of N,N,N-trimethyl-N-2-methacryloyloxyethylammonium chloride, and 1 mmol of 2,2'-azobis(2-amidinopropane) dihydrochloride were added. The monomer composition containing the monomer composition was weighed out into ion-exchanged water so that the solid content was 5% by weight.
  • the mixture was stirred at 200 rpm and polymerized at 70° C. for 24 hours under a nitrogen atmosphere. After the reaction was completed, it was freeze-dried to obtain insulating particles (average particle diameter 220 nm, CV value 10%) having ammonium groups on the surface.
  • the obtained insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of insulating particles.
  • Nickel plating solution (pH 8.0) containing 0.14 mol/L of nickel sulfate, 1.45 mol/L of hydrazine, 0.90 mol/L of sodium stannate trihydrate, and 0.60 mol/L of sodium gluconate. prepared.
  • electroless nickel-tin alloy plating was performed at 58 ° C. using this nickel plating solution instead of nickel plating solutions (1), (2), and (3). Conductive particles were obtained.
  • Nickel plating solution (pH 8.5) containing nickel sulfate 0.14 mol/L, hydrazine 1.05 mol/L, sodium stannate trihydrate 0.30 mol/L, and sodium gluconate 0.30 mol/L prepared.
  • electroless nickel-tin alloy plating was performed at 65 ° C. using this nickel plating solution instead of nickel plating solutions (1), (2), and (3). Conductive particles were obtained.
  • the average content of nickel and tin, the maximum value of the content of tin in the above region R1, and the maximum value of the content of tin in the above region R2 were determined.
  • the content of tin in region R1 was determined out of the total 100% by weight of tin contained in the entire Ni--Sn conductive layer.
  • the region where the maximum value of the tin content exists is investigated, and the proportion of the region containing tin in the 100% thickness of the Ni-Sn conductive layer is determined. I asked for
  • a transparent glass substrate having an ITO electrode pattern with L/S of 20 ⁇ m/20 ⁇ m on the top surface was prepared. Further, a semiconductor chip having a gold electrode pattern with L/S of 20 ⁇ m/20 ⁇ m on the lower surface was prepared.
  • the anisotropic conductive paste was applied to a thickness of 30 ⁇ m on the transparent glass substrate to form an anisotropic conductive paste layer.
  • the semiconductor chips were stacked on the anisotropic conductive paste layer so that the electrodes faced each other.
  • a pressure heating head is placed on the top surface of the semiconductor chip, and a pressure of 1 MPa is applied to the anisotropic conductive paste layer. It was cured at 185°C to obtain a connected structure.
  • connection resistance between the upper and lower electrodes of the obtained connected structure was measured by a four-terminal method.
  • the initial connection resistance (A) was determined based on the following criteria.
  • connection resistance is 2.0 ⁇ or less
  • Connection resistance is over 2.0 ⁇ and 3.0 ⁇ or less
  • Connection resistance is over 3.0 ⁇ and 5.0 ⁇ or less
  • Connection resistance is 5.0 ⁇ exceeds 10 ⁇ or less
  • connection resistance (B) after being exposed to the presence of acid The obtained conductive particles were immersed in an 8% sulfuric acid aqueous solution at room temperature (23° C.) for 45 minutes. Thereafter, the particles were taken out by filtration, washed with water, replaced with ethanol, and allowed to stand for 10 minutes to dry the particles, thereby obtaining conductive particles exposed to acid.
  • a connected structure was produced using the obtained conductive particles in the same manner as in (2) above, and the connection resistance was measured in the same manner as the initial connection resistance (A).
  • the connection resistance (B) after being exposed to the presence of acid was determined based on the following criteria.
  • Connection resistance B is 1.0 times or more and less than 1.5 times the connection resistance A, and 10 ⁇ or less ⁇ : Connection resistance B is 1.5 times or more and less than 2.0 times the connection resistance A , and 10 ⁇ or less ⁇ : Connection resistance B is 2.0 times or more and less than 5.0 times the connection resistance A, and 10 ⁇ or less ⁇ : Connection resistance B is 5.0 times or more and less than 10 times the connection resistance A , and 10 ⁇ or less ⁇ : Connection resistance B is 10 times or more than connection resistance A, or exceeds 10 ⁇

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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Abstract

L'invention concerne des particules électroconductrices qui peuvent réduire une résistance de connexion lorsque des électrodes sont électriquement connectées l'une à l'autre, et peuvent empêcher le transfert de charges dans une couche électroconductrice Ni-Sn même lorsqu'elles sont exposées à une haute tension pendant une longue période dans un environnement à haute température et à humidité élevée.　Chacune des particules électroconductrices selon la présente invention comprend une particule de base et une couche électroconductrice Ni-Sn contenant du nickel et de l'étain, la couche électroconductrice Ni-Sn étant disposée sur la surface de la particule de base, la teneur moyenne en étain dans toute la région de la couche électroconductrice Ni-Sn étant inférieure à 5 % en poids, et la valeur la plus grande de la teneur en étain dans une région correspondant à une moitié externe dans la direction de l'épaisseur de la couche électroconductrice Ni-Sn étant de 5 % en poids ou plus lorsque la teneur en étain est mesurée dans la direction de l'épaisseur de la couche électroconductrice Ni-Sn par TEM-EDX.
PCT/JP2023/027151 2022-08-08 2023-07-25 Particules électriquement conductrices, matériau électriquement conducteur et structure de connexion WO2024034386A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015130328A (ja) * 2013-12-03 2015-07-16 積水化学工業株式会社 導電性粒子、導電材料及び接続構造体
WO2017138521A1 (fr) * 2016-02-08 2017-08-17 積水化学工業株式会社 Particules conductrices, matériau conducteur et structure connectée

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015130328A (ja) * 2013-12-03 2015-07-16 積水化学工業株式会社 導電性粒子、導電材料及び接続構造体
WO2017138521A1 (fr) * 2016-02-08 2017-08-17 積水化学工業株式会社 Particules conductrices, matériau conducteur et structure connectée

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