WO2013042785A1 - Particules fines électro-conductrices et matériau conducteur anisotrope en contenant - Google Patents

Particules fines électro-conductrices et matériau conducteur anisotrope en contenant Download PDF

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WO2013042785A1
WO2013042785A1 PCT/JP2012/074293 JP2012074293W WO2013042785A1 WO 2013042785 A1 WO2013042785 A1 WO 2013042785A1 JP 2012074293 W JP2012074293 W JP 2012074293W WO 2013042785 A1 WO2013042785 A1 WO 2013042785A1
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Prior art keywords
particles
fine particles
conductive fine
conductive
nickel
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PCT/JP2012/074293
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English (en)
Japanese (ja)
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木太　純子
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株式会社日本触媒
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Priority to JP2013504044A priority Critical patent/JP5245021B1/ja
Priority to CN201280046185.9A priority patent/CN103827981A/zh
Priority to KR1020147007624A priority patent/KR20140054337A/ko
Publication of WO2013042785A1 publication Critical patent/WO2013042785A1/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
    • 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
    • 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
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • H01B17/64—Insulating bodies with conductive admixtures, inserts or layers
    • 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 fine particles including a nickel layer as a conductive metal layer, and particularly to conductive fine particles having excellent nickel layer flexibility.
  • An anisotropic conductive material is a material in which conductive fine particles are mixed with a binder resin, for example, anisotropic conductive paste (ACP), anisotropic conductive film (ACF), anisotropic conductive ink, anisotropic conductive.
  • ACP anisotropic conductive paste
  • ACF anisotropic conductive film
  • anisotropic conductive ink anisotropic conductive.
  • conductive fine particles used for the anisotropic conductive material metal particles or those obtained by coating the surface of resin particles serving as a substrate with a conductive metal layer are used.
  • Patent Document 1 includes base particles containing a resin and Ni or the like (excluding Ni—P alloy) formed on the surface of the base particles.
  • a conductive fine particle including a buffer layer and an Au layer formed on the buffer layer wherein the buffer layer has a crystallite diameter of 300 nm or less.
  • the buffer layer is formed by a sputtering method.
  • Ni—P layer, Ni—B layer, and Ni—P—B layer formed by electroless plating are peeled off during pressure bonding even when the crystallite diameter is 300 nm or less.
  • Patent Document 1 See Table 1.
  • the present inventor has examined the compressive deformation behavior of the conductive fine particles having a nickel layer.
  • the inflection point is It was confirmed to appear.
  • This inflection point is caused by the destruction or damage of the nickel layer itself formed on the surface of the base particle, and is considered to be a behavior that the conductive metal layer including the nickel layer shows independently.
  • the compression displacement (%) at which this inflection point is observed tends to be small and the connection resistance value tends to be high.
  • This invention is made
  • the conductive fine particles of the present invention that can solve the above-mentioned problems are conductive fine particles having base particles and a conductive metal layer that covers the surface of the base particles, and the conductive metal layer Is characterized by including a nickel plating layer and having a crystallite diameter in the [111] direction of nickel measured by a powder X-ray diffraction method of 3 nm or less.
  • the compression load value is lower than the compression load value at the breaking point (Y) at which the base particle breaks.
  • the compression deformation rate at the break point (Y) is L2
  • the compression deformation rate at the inflection point (X) is L1
  • the ratio (L1 / L2) is preferably 0.3 or more.
  • the L2 is preferably 35% to 70%.
  • the L2 is preferably 35% to 70%.
  • the crystallite diameter in the [111] direction of the nickel is preferably 1.5 nm or more.
  • the number average particle diameter of the substrate particles is preferably 50 ⁇ m or less, and the aspect in which the number average particle diameter is 3 ⁇ m or less and the aspect in which the number average particle diameter is 8 ⁇ m or more are also preferable aspects of the present invention.
  • 10% K value of the base particle is 500 N / mm 2 or more, preferably 30000 N / mm 2 or less.
  • the present invention also includes an anisotropic conductive material containing the conductive fine particles.
  • the present invention by controlling the crystallite diameter in the nickel layer, the flexibility (extensibility) of the nickel layer can be improved. Thereby, even when the nickel layer is broken, the cracks are fine, and it is easy to follow the deformation of the base material particles, and the peeling is suppressed. Therefore, the conductive fine particles of the present invention can realize a lower connection resistance value. Furthermore, since the difference between the compressive deformation rate (L1) at which the nickel layer breaks and the compressive deformation rate (L2) at which the substrate particles break down can be reduced simply by controlling the crystallite diameter, the substrate having various hardnesses. Particles can be employed, and particle design is facilitated.
  • the compression displacement curve of the electroconductive fine particles of this invention is shown.
  • the change of resistance value when the particle diameter and crystallite diameter of the electroconductive fine particles of this invention are changed is shown.
  • the conductive fine particles of the present invention have base material particles and a conductive metal layer that covers the surface of the base material particles.
  • the conductive metal layer includes a nickel layer, and the crystallite diameter perpendicular to the nickel lattice plane (111) measured by powder X-ray diffraction (hereinafter, this is expressed as the crystallite diameter in the [111] direction). And may be simply referred to as “crystallite diameter.”) Is 3 nm or less, preferably 2.9 nm or less, more preferably 2.8 nm or less. The smaller the crystallite diameter, the more flexible (extensibility) of the nickel layer.
  • the lower limit of the crystallite diameter is not particularly limited, but is preferably 1 nm or more, more preferably 1.1 nm or more, still more preferably 1.2 nm or more, and still more preferably 1 because the electric resistance value at the crystallite interface can be reduced. .5 nm or more, more preferably 1.7 nm or more. In particular, if the crystallite diameter is 1.5 nm or more, the electrical resistance value is hardly increased due to the influence of humidity in the air, and the moisture resistance of the conductive fine particles is maintained. A method for measuring the crystallite diameter will be described later.
  • the nickel layer is made of nickel or a nickel alloy.
  • the nickel content in the nickel alloy is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 82% by mass or more.
  • the nickel alloy include Ni—Au, Ni—Pd, Ni—Pd—Au, Ni—Ag, Ni—P, Ni—B, Ni—Zn, Ni—Sn, Ni—W, Ni—Co, and Ni—. W, Ni—Ti, and the like are preferable, and among these, a Ni—P alloy is preferable.
  • the P concentration in the nickel alloy is preferably 18% by mass or less, more preferably 16% by mass or less, still more preferably 14% by mass or less, and particularly preferably 9.5% by mass or less.
  • the lower the P concentration the lower the electrical resistance value of the nickel layer.
  • the P concentration is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more.
  • concentration shows ratio (P / (P + Ni)) of P mass with respect to the total mass of Ni and P in a nickel alloy in percentage.
  • P concentration affects the hardness of the nickel layer.
  • the crystallite diameter in the [111] direction is 3 nm or less. The effect becomes more remarkable.
  • the thickness of the nickel layer is preferably 0.02 ⁇ m or more, more preferably 0.05 ⁇ m or more, further preferably 0.07 ⁇ m or more, preferably 0.3 ⁇ m or less, more preferably 0.25 ⁇ m or less, still more preferably Is 0.2 ⁇ m or less.
  • the conductivity of the conductive fine particles becomes better.
  • the thickness of the nickel layer is 0.3 ⁇ m or less, the density of the conductive fine particles does not become too high, and sedimentation when dispersed in a binder or the like is suppressed, and the dispersion stability is improved.
  • the grain boundary structure appearing on the fracture surface in the thickness direction of the nickel layer is not particularly limited. That is, if the crystallite diameter is 3 nm or less, the flexibility of the nickel layer is improved regardless of the grain boundary structure.
  • the grain boundary structure of the nickel layer when the cross section in the thickness direction is observed at a magnification of 100000 times using a scanning electron microscope, the grain boundaries are oriented (oriented orientation), grain boundaries Are not oriented (non-oriented), and the grain boundary is not confirmed.
  • the grain boundaries are oriented, a plurality of linear grain boundaries are arranged in parallel. In this case, the direction of the straight grain boundary includes the thickness direction, the layer direction, and the oblique direction of the nickel layer.
  • a group of grain boundaries oriented in a specific direction is viewed as one series
  • Such series may be arranged in the thickness direction of the nickel layer, or may be arranged in the layer direction of the nickel layer.
  • an aspect in which the alignment direction of the series adjacent to the thickness direction is line-symmetric with respect to these boundaries as the symmetry axis.
  • the conductive fine particle is formed of only the nickel layer as a conductive metal layer is a preferred embodiment of the conductive fine particle of the present invention.
  • another conductive metal layer may be used.
  • a form in which the conductive metal layer is formed by laminating the nickel layer and another conductive metal layer is also one form of a preferred embodiment of the conductive fine particles of the present invention.
  • a metal which comprises other electroconductive metal layers For example, gold, silver, copper, platinum, iron, lead, aluminum, chromium, palladium, rhodium, ruthenium, antimony, bismuth, germanium, tin, cobalt Indium, nickel-phosphorus, nickel-boron and other metals and metal compounds, and alloys thereof.
  • the nickel layer may be formed directly on the base particle, or another conductive metal layer may be formed on the base particle surface as a base, and the nickel layer may be formed thereon. It is preferable to form directly on.
  • the conductive metal layer is preferably a combination of nickel layer-gold layer, nickel layer-palladium layer, nickel layer-palladium layer-gold layer, nickel layer-silver layer, and the like. In particular, it is preferable to have a gold layer or a palladium layer as the outermost layer.
  • the thickness of the other conductive metal layer is preferably thinner than the nickel layer. Specifically, the thickness of the other conductive metal layer is preferably 3/4 or less of the thickness of the nickel layer, more preferably 1/2 or less, and even more preferably 1/3 or less.
  • the conductive fine particles may be further subjected to surface treatment as necessary in order to prevent corrosion of the conductive metal layer, prevent oxidation, and prevent discoloration.
  • a metal oxide layer containing cerium or titanium is formed on the surface of the nickel layer; having an alkyl group having 3 to 22 carbon atoms Surface treatment with a compound; and the like.
  • the thickness of the conductive metal layer is preferably 0.02 ⁇ m or more, more preferably 0.05 ⁇ m or more, and still more preferably 0.00. It is 0.7 ⁇ m or more, preferably 0.3 ⁇ m or less, more preferably 0.25 ⁇ m or less, and still more preferably 0.2 ⁇ m or less.
  • the thickness of the conductive metal is within the above range, conductive fine particles having excellent dispersion stability in a binder and the like and excellent conductivity can be obtained.
  • the number average particle diameter of the conductive fine particles is preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, further preferably 2 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less. .
  • the number-based variation coefficient (CV value) of the conductive fine particles is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less.
  • the conductive fine particles of the present invention can achieve a low connection resistance value because the nickel layer has a predetermined crystallite diameter and the nickel layer is highly flexible. Therefore, the number average particle diameter is preferably less than 10 ⁇ m, more preferably 9.5 ⁇ m or less, further preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m, for the reason that the effect of the present invention becomes more remarkable. Hereinafter, it is particularly preferably 2.8 ⁇ m or less, and most preferably 2.3 ⁇ m or less. Details will be described when the number average particle diameter of the base particles is described.
  • the number average particle diameter of the conductive fine particles is preferably 3.3 ⁇ m or less, more preferably 3.0 ⁇ m or less, and even more preferably 2.7 ⁇ m or less. It is 3 ⁇ m or more, preferably 1.8 ⁇ m or more, and more preferably 2.3 ⁇ m or more.
  • the conductive fine particles having the average particle diameter of the conductive fine particles of 8.3 ⁇ m or more have a specific problem regarding the resistance value at the time of high compression connection, According to the present invention, the problem can be solved. Therefore, even when the number average particle diameter of the conductive fine particles is, for example, 8.3 ⁇ m or more, more preferably 9.3 ⁇ m or more, the effect of the present invention can be effectively used.
  • An upper limit becomes like this. Preferably it is 25 micrometers or less, More preferably, it is 18 micrometers or less, More preferably, it is 14 micrometers or less.
  • the conductive fine particles exhibit the following fracture behavior in a compression test in which the conductive fine particles are compressed at a load load rate of 2.2295 mN / sec.
  • FIG. 1 shows a compression displacement curve of the conductive fine particles of the present invention.
  • the compression displacement curve is the relationship between the load when the load applied to the particle is increased at a constant speed and compressed (ie, the cumulative load from the start of particle compression to that point) and the deformation rate of the particle Are plotted.
  • the conductive fine particles of the present invention have an inflection point (X) due to the destruction of the nickel layer at a compression load value lower than the compression load value at the break point (Y) at which the base particle breaks in the compression displacement curve. Is confirmed.
  • the ratio (L1 / L2) is 0.3 or more. Preferably, it is 0.35 or more, more preferably 0.4 or more.
  • the upper limit of the ratio (L1 / L2) is not particularly limited, but is naturally less than 1.
  • the flexibility of the nickel layer can be improved by setting the crystallite diameter within the above range. Therefore, even when using highly flexible base particles, the nickel layer can be effectively prevented from peeling. Therefore, the room for selection of substrate particles is widened, and particle design is facilitated.
  • the base material particles having high flexibility those having L2 of 35% or more are preferable, more preferably 40% or more, still more preferably 45% or more, and those having 70% or less are more preferable, and 67% are more preferable. Hereinafter, it is more preferably 65% or less.
  • the ratio (P1 / P2) is preferably 0.3 or more, More preferably, it is 0.38 or more, More preferably, it is 0.4 or more.
  • the upper limit of the ratio (P1 / P2) is not particularly limited, but is usually less than 1.
  • the conductive fine particles of the present invention are suitably used for anisotropic conductive materials such as conductive spacers for LCD, anisotropic conductive films, anisotropic conductive pastes, anisotropic conductive adhesives, and anisotropic conductive inks. Can do.
  • the base particles are preferably resin particles containing a resin component.
  • resin particles By using resin particles, conductive fine particles having excellent elastic deformation characteristics can be obtained.
  • the resin particles include amino resins such as melamine formaldehyde resin, melamine-benzoguanamine-formaldehyde resin, urea formaldehyde resin; vinyl polymers such as styrene resin, acrylic resin, styrene-acrylic resin; polyethylene, polypropylene, poly Polyolefins such as vinyl chloride, polytetrafluoroethylene, polyisobutylene, and polybutadiene; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonates; polyamides; polyimides; phenol formaldehyde resin; The material which comprises these resin particles may be used independently, and 2 or more types may be used together.
  • vinyl polymers, amino resins, and organosiloxanes are preferable, and vinyl polymers and amino resins are preferable in that the effect obtained by setting the crystallite diameter of nickel in the [111] direction to 3 nm or less is more remarkable. Is more preferable, and a vinyl polymer is particularly preferable.
  • a material containing a vinyl polymer has an organic skeleton formed by polymerizing vinyl groups, and is excellent in elastic deformation during pressure connection.
  • a vinyl polymer containing divinylbenzene and / or di (meth) acrylate as a polymerization component has little decrease in particle strength after coating with a conductive metal.
  • Vinyl polymer particles are composed of a vinyl polymer.
  • Vinyl polymers can be formed by polymerizing (radical polymerization) vinyl monomers (vinyl group-containing monomers). These vinyl monomers are vinyl crosslinkable monomers and vinyl noncrosslinkable monomers. Divided into monomers.
  • the “vinyl group” includes not only a carbon-carbon double bond but also a functional group such as (meth) acryloxy group, allyl group, isopropenyl group, vinylphenyl group, isopropenylphenyl group, and polymerizable carbon- Substituents composed of carbon double bonds are also included.
  • (meth) acryloxy group “(meth) acrylate” and “(meth) acryl” are “acryloxy group and / or methacryloxy group”, “acrylate and / or methacrylate” and “acryl and / Or methacryl ".
  • the vinyl-based crosslinkable monomer has a vinyl group and can form a crosslinked structure, and specifically, a monomer (monomer having two or more vinyl groups in one molecule). (1)), or having one vinyl group and a binding functional group other than a vinyl group in one molecule (such as a carboxyl group, a protonic hydrogen-containing group such as a hydroxy group, or a terminal functional group such as an alkoxy group).
  • a monomer (monomer (2)) is mentioned.
  • Examples of the monomer (1) (monomer having two or more vinyl groups in one molecule) among the vinyl-based crosslinkable monomers include, for example, allyl (meth) acrylate such as allyl (meth) acrylate. ) Acrylates; alkanediol di (meth) acrylate (for example, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,3-butylene di (meth) acrylate, etc.), polyalkylene glycol di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, decaethylene glycol di (Meth) acrylate, pentade
  • (meth) acrylates (polyfunctional (meth) acrylate) having two or more (meth) acryloyl groups in one molecule and aromatic hydrocarbon crosslinking agents (especially styrene polyfunctional monomers) are included. preferable.
  • (meth) acrylates (polyfunctional (meth) acrylate) having two or more (meth) acryloyl groups in one molecule (meth) having two (meth) acryloyl groups in one molecule
  • Acrylate (di (meth) acrylate) is particularly preferable, and among them, acrylate (diacrylate) having two acryloyl groups in one molecule is preferable.
  • the styrenic polyfunctional monomers monomers having two vinyl groups in one molecule such as divinylbenzene are preferable.
  • a monomer (1) may be used independently and may use 2 or more types together.
  • the monomer (2) (monomer having one vinyl group and a binding functional group other than vinyl group in one molecule) is, for example, (meth) Monomers having a carboxyl group such as acrylic acid; hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, p -Monomers having hydroxy groups such as hydroxy group-containing styrenes such as hydroxystyrene; alkoxy groups such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 2-butoxyethyl (meth) acrylate Containing alkoxy groups such as (meth) acrylates and alkoxystyrenes such as p-methoxystyrene And the like; monomers.
  • a monomer (2) may be used independently
  • the vinyl-based non-crosslinkable monomer is a monomer having one vinyl group in one molecule (monomer (3)) or the monomer in the case where there is no counterpart monomer (2) (monomer having one vinyl group and a binding functional group other than vinyl group in one molecule).
  • the monomer (3) (monomer having one vinyl group in one molecule) includes (meth) acrylate monofunctional monomers and styrene monofunctional monomers. Monomers are included. Examples of the (meth) acrylate monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate.
  • Styrene monofunctional monomers include styrene; alkyl styrenes such as o-methyl styrene, m-methyl styrene, p-methyl styrene, ⁇ -methyl styrene, ethyl styrene (ethyl vinyl benzene), pt-butyl styrene, Examples include halogen group-containing styrenes such as o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene, and styrene is preferred.
  • a monomer (3) may be used independently and may use 2 or more types together.
  • the vinyl monomer preferably includes at least the vinyl crosslinkable monomer (1).
  • the vinyl crosslinkable monomer (1) and the vinyl noncrosslinkable monomer ( 3) (in particular, a copolymer of the monomer (1) and the monomer (3)) is preferable.
  • an embodiment including at least one selected from a styrene monofunctional monomer, a styrene polyfunctional monomer, and a polyfunctional (meth) acrylate as a constituent component is preferable.
  • the styrene monofunctional monomer is preferably styrene
  • the styrene polyfunctional monomer is preferably divinylbenzene
  • the polyfunctional meta (acrylate) is preferably di (meth) acrylate.
  • an embodiment having divinylbenzene and di (meth) acrylate as essential components; an embodiment having divinylbenzene and styrene as essential components; and an embodiment having di (meth) acrylate and styrene as essential components are particularly preferable.
  • the ratio of the crosslinkable monomer (total of vinyl-based crosslinkable monomer and silane-based crosslinkable monomer) in the total monomers constituting the vinyl polymer particles is excellent in elastic deformation and restoring force. Therefore, 20 mass% or more is preferable, More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more. When the ratio of the crosslinkable monomer is within the above range, the restoring force can be improved while maintaining excellent elastic deformation characteristics.
  • the upper limit of the ratio of the crosslinkable monomer is not particularly limited, but depending on the type of the crosslinkable monomer used, if the ratio of the crosslinkable monomer is too large, it becomes too hard and compressively deforms during anisotropic conductive connection.
  • the proportion of the crosslinkable monomer is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
  • the 10% K value of the base particle can be reduced as the proportion of the crosslinkable monomer is reduced.
  • the proportion of the crosslinkable monomer may be 50% by mass or less, 40% by mass or less, and 30% by mass or less.
  • the vinyl polymer particles may contain other components to the extent that the properties of the vinyl polymer are not impaired.
  • the vinyl polymer particles preferably contain 50% by mass or more of the vinyl polymer, more preferably 60% by mass or more, and still more preferably 70% by mass or more.
  • a polysiloxane component is preferable.
  • the polysiloxane skeleton can be formed by using a silane monomer, and the silane monomer is divided into a silane crosslinkable monomer and a silane noncrosslinkable monomer. Moreover, when a silane crosslinkable monomer is used as the silane monomer, a crosslinked structure can be formed.
  • the cross-linked structure formed by the silane cross-linkable monomer includes a cross-link between a vinyl polymer and a vinyl polymer (first form); a cross-link between a polysiloxane skeleton and a polysiloxane skeleton (second In which the vinyl polymer skeleton and the polysiloxane skeleton are cross-linked (third form).
  • silane-based crosslinkable monomer that can form the first form (crosslinking between vinyl polymers) include silane compounds having two or more vinyl groups such as dimethyldivinylsilane, methyltrivinylsilane, and tetravinylsilane. Can be mentioned.
  • silane crosslinkable monomer that can form the second form (crosslink between polysiloxanes) include tetrafunctional silane single monomers such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane.
  • Examples of the polymer include trifunctional silane monomers such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.
  • Examples of silane crosslinkable monomers that can form the third form (crosslinking between vinyl polymer and polysiloxane) include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- (Meth) acryloyl such as acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxyethoxypropyltrimethoxysilane Di- or trialkoxysilane having a group; di- or trialkoxysilane having a vinyl group such as vinyltri
  • silane-based non-crosslinkable monomer examples include bifunctional silane-based monomers such as dimethyldimethoxysilane and dialkylsilane such as dimethyldiethoxysilane; and trialkylsilanes such as trimethylmethoxysilane and trimethylethoxysilane. And monofunctional silane-based monomers. These silane non-crosslinkable monomers may be used alone or in combination of two or more.
  • the polysiloxane skeleton is preferably a skeleton derived from a polymerizable polysiloxane having a radical-polymerizable carbon-carbon double bond (for example, a vinyl group such as a (meth) acryloyl group). That is, the polysiloxane skeleton is a silane crosslinkable monomer (preferably having a (meth) acryloyl group) capable of forming at least the third form (crosslinking between vinyl polymer and polysiloxane) as a constituent component.
  • a silane crosslinkable monomer preferably having a (meth) acryloyl group
  • it is a polysiloxane skeleton formed by hydrolysis and condensation of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane).
  • the amount of the vinyl monomer used is preferably 100 parts by mass or more, more preferably 200 parts by mass or more with respect to 100 parts by mass of the silane monomer. More preferably, it is 300 parts by mass or more, preferably 700 parts by mass or less, more preferably 600 parts by mass or less, and still more preferably 500 parts by mass or less.
  • the vinyl polymer particles can be produced, for example, by polymerizing a vinyl monomer. Specifically, (i) a monomer composition containing a vinyl monomer as a polymerization component is used. A conventionally known method of aqueous suspension polymerization, dispersion polymerization, emulsion polymerization; (ii) after obtaining a vinyl group-containing polysiloxane using a silane monomer, the vinyl group-containing polysiloxane and the vinyl group Polymerization (radical polymerization) with a monomer; (iii) a so-called seed polymerization method in which a vinyl monomer is radically polymerized after the vinyl monomer is absorbed into the seed particles.
  • the silane compound which has vinyl groups such as the said silane compound which has two or more vinyl groups, and the di- or trialkoxysilane which has a vinyl group as a vinyl-type monomer.
  • vinyl polymer particles into which a polysiloxane skeleton is introduced can be obtained by using a silane-based crosslinkable monomer capable of forming at least the third form.
  • non-crosslinked or low-crosslinked polystyrene particles or polysiloxane particles it is preferable to use non-crosslinked or low-crosslinked polystyrene particles or polysiloxane particles as seed particles.
  • polysiloxane particles By using polysiloxane particles as seed particles, a polysiloxane skeleton can be introduced into the vinyl polymer.
  • the resulting vinyl polymer particles are particularly excellent in elastic deformation and contact pressure because the vinyl polymer and the polysiloxane skeleton are bonded via the silicon atoms constituting the polysiloxane. It will be a thing.
  • the vinyl group-containing polysiloxane particles can be produced, for example, by (co) hydrolytic condensation of a silane monomer (mixture) containing a vinyl group-containing di- or trialkoxysilane.
  • the base particles are subjected to heat treatment.
  • the heat treatment is preferably performed in an air atmosphere or an inert atmosphere, and more preferably performed in an inert atmosphere (for example, in a nitrogen atmosphere).
  • the temperature of the heat treatment is preferably 120 ° C. (more preferably 180 ° C., more preferably 200 ° C.) or more, and preferably a thermal decomposition temperature (more preferably 350 ° C., more preferably 330 ° C.) or less.
  • the heat treatment time is preferably 0.3 hours (more preferably 0.5 hours, more preferably 0.7 hours) or more, and preferably 10 hours (more preferably 5.0 hours, still more preferably 3.0 hours). The following are preferred.
  • the amino resin particles are preferably composed of a condensate of an amino compound and formaldehyde.
  • the amino compounds include benzoguanamine, cyclohexanecarboguanamine, cyclohexenecarboguanamine, acetoguanamine, norbornenecarboguanamine, guanamine compounds such as spiroguanamine, and polyfunctional amino compounds such as compounds having a triazine ring structure such as melamine. .
  • polyfunctional amino compounds are preferable, compounds having a triazine ring structure are more preferable, and melamine and guanamine compounds (particularly benzoguanamine) are particularly preferable.
  • the amino compound may be used alone or in combination of two or more.
  • the amino resin particles preferably contain 10% by mass or more of a guanamine compound in the amino compound, more preferably 20% by mass or more, and still more preferably 50% by mass or more.
  • a guanamine compound in the amino compound is within the above range, the particle size distribution is sharper and the particle size is precisely controlled.
  • Amino resin particles can be obtained, for example, by reacting an amino compound and formaldehyde in an aqueous medium (addition condensation reaction). Usually, this reaction is carried out under heating (50 to 100 ° C.). Further, the degree of crosslinking can be increased by carrying out the reaction in the presence of an acid catalyst such as dodecylbenzenesulfonic acid or sulfuric acid.
  • an acid catalyst such as dodecylbenzenesulfonic acid or sulfuric acid.
  • Examples of the method for producing amino resin particles include, for example, JP-A No. 2000-256432, JP-A No. 2002-293854, JP-A No. 2002-293855, JP-A No. 2002-293856, and JP-A No. 2002-293857.
  • the polyfunctional amino compound and formaldehyde are reacted (addition condensation reaction) in an aqueous medium (preferably a basic aqueous medium) to form a condensate oligomer, and the condensate oligomer is dissolved or dispersed.
  • Crosslinked amino resin particles can be produced by mixing and curing an acid catalyst such as dodecylbenzenesulfonic acid or sulfuric acid in the aqueous medium. It is preferable that both the step of forming the condensate oligomer and the step of forming the amino resin having a crosslinked structure are carried out in a heated state at a temperature of 50 to 100 ° C.
  • amino resin particles having a sharp particle size distribution can be obtained by performing the addition condensation reaction in the presence of a surfactant.
  • Organosiloxane Particles Organopolysiloxane particles (co) hydrolyze one or more silane monomers (silane crosslinkable monomers, silane noncrosslinkable monomers) that do not contain vinyl groups. Obtained by condensation.
  • silane monomers silane crosslinkable monomers, silane noncrosslinkable monomers
  • examples of the silane monomer not containing a vinyl group include trifunctional silane monomers such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and phenyltrimethoxysilane.
  • Di- or trialkoxysilanes having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;
  • Examples thereof include di- or trialkoxysilanes having an amino group such as propyltrimethoxysilane and 3-aminopropyltriethoxysilane.
  • 10% K value of the base material particles 500 N / mm 2 or more, preferably 30000 N / mm 2 or less. If the 10% K value of the substrate particles is too small, the connection resistance is low due to the fact that the surrounding binder cannot be sufficiently removed when used as an anisotropic conductive material, and the degree of biting into the electrode is weak. There is a possibility that the value cannot be obtained. On the other hand, if the 10% K value of the base particles is too large, there is a possibility that an electrically good contact state cannot be secured with respect to the connection site. 10% K value of the substrate particles is 1000 N / mm 2 or more, more preferably 27000N / mm 2 or less.
  • the 10% K value of the base particle is a compression elastic modulus when the particle is compressed by 10% (when the diameter of the particle is displaced by 10%).
  • a known micro compression tester manufactured by Shimadzu Corporation
  • MCT-W500 “etc.”
  • the load when the particles are deformed until the compression displacement becomes 10% of the particle diameter by applying a load at room temperature at a load load rate of 2.2295 mN / sec at room temperature.
  • the load (N) and the amount of displacement (compression displacement: mm) can be measured and determined based on the following formula.
  • E compression elastic modulus (N / mm 2 )
  • F compression load (N)
  • S compression displacement (mm)
  • R radius of particle (mm)
  • the number average particle diameter of the substrate particles is preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, further preferably 2 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and still more preferably. 30 ⁇ m or less.
  • the number-based variation coefficient (CV value) of the particle diameter of the substrate particles is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. As described above, when the conductive fine particles are fine (specifically, the number average particle diameter is less than 10.0 ⁇ m), the effect of the present invention becomes more remarkable.
  • the number average particle size of the base particles is preferably less than 10.0 ⁇ m, more preferably 9.5 ⁇ m or less, further preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less, still more preferably 3 ⁇ m or less, and even more preferably. It is 2.8 ⁇ m or less, particularly preferably 2.6 ⁇ m or less.
  • the number average particle diameter of the base particles is preferably 3 ⁇ m or less, more preferably 2.7 ⁇ m or less, and even more preferably 2.4 ⁇ m or less.
  • the nickel layer is formed during high compression connection.
  • the lower limit of the number average particle diameter is, for example, 1 ⁇ m or more, preferably 1.5 ⁇ m or more, and more preferably 2.0 ⁇ m or more.
  • the 10% K value of the base particles is preferably 3000 N / mm 2 or more and 30000 or less from the viewpoint of reducing the load on the nickel layer with such a fine particle size.
  • the base particles is 4000 N / mm ⁇ 2 > or more, More preferably, it is 5000 N / mm ⁇ 2 > or more.
  • setting the base particles to a medium particle size that is, a number average particle size of 8 ⁇ m or more, more preferably 9 ⁇ m or more is also an embodiment in which the effect of the present invention can be effectively used.
  • the crystallite diameter of nickel is 3 nm or less, the nickel layer becomes flexible and can follow up to a large deformation range of the base particles (as a result, the ratio (L1 / L2) increases).
  • the 10% K value of the base particle is small from the viewpoint of enabling large deformation at such a medium particle size.
  • 10% K value when the number average particle size of the substrate particles than 8 ⁇ m for example, 6000 N / mm 2 or less, preferably 5000N / mm 2, more preferably not more than 4000 N / mm 2.
  • the conductive fine particles of the present invention can be produced by an electroless plating method.
  • an electroless plating method By controlling the kind and concentration of the complexing agent in the nickel plating solution, the temperature of the nickel plating solution, etc.
  • the diameter can be controlled.
  • Specific examples of the manufacturing method include a manufacturing method having a first electroless plating step and a second electroless plating step (aspect 1); a manufacturing method having an electroless plating step performed using a specific plating solution (aspect 2) ;
  • the manufacturing method of the aspects 1 and 2 is demonstrated.
  • the base material particles subjected to the electroless plating process are subjected to a catalytic treatment.
  • the base particle itself does not have hydrophilicity and adhesion with the conductive metal layer is not good, it is preferable to provide an etching treatment step before the catalyzing step.
  • Etching treatment In the etching treatment process, oxidizing agents such as chromic acid, chromic anhydride-sulfuric acid mixture, permanganic acid; strong acids such as hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid; strong alkaline solutions such as sodium hydroxide and potassium hydroxide Using other commercially available etching agents, etc., to impart hydrophilicity to the surface of the substrate particles and to improve the wettability to the subsequent electroless plating solution. Further, minute unevenness is formed, and the adhesion between the substrate particles after electroless plating described later and the conductive metal layer is improved by the anchor effect of the unevenness.
  • oxidizing agents such as chromic acid, chromic anhydride-sulfuric acid mixture, permanganic acid
  • strong acids such as hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid
  • strong alkaline solutions such as sodium hydroxide and potassium hydroxide
  • Catalytic treatment In the catalytic treatment, after precious metal ions are captured on the surface of the base material particles, they are reduced and supported on the surface of the base material particles, and the surface of the base material particles is subjected to electroless plating in the next step. A catalyst layer that can serve as a starting point is formed.
  • the substrate particles themselves do not have the ability to capture noble metal ions it is also preferable to perform a surface modification treatment before the catalytic conversion.
  • the surface modification treatment can be performed by bringing the substrate particles into contact with water or an organic solvent in which the surface treatment agent is dissolved.
  • the etched base particles are immersed in a dilute acidic aqueous solution of a noble metal salt such as palladium chloride or silver nitrate, and then the base particles are separated and washed with water. Subsequently, the resultant is dispersed in water, and a reducing agent is added thereto to reduce the noble metal ions.
  • a noble metal salt such as palladium chloride or silver nitrate
  • the resultant is dispersed in water, and a reducing agent is added thereto to reduce the noble metal ions.
  • the reducing agent include sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, hydrazine, formalin and the like.
  • a reducing agent may be used individually by 1 type, and may use 2 or more types together.
  • the base particles are brought into contact with the solution containing tin ions (Sn 2+ ) to adsorb the tin ions on the surface of the base particles and subjected to sensitization treatment, and then the solution containing palladium ions (Pd 2+ ) is added.
  • the solution containing tin ions Sn 2+
  • Pd 2+ palladium ions
  • a method of depositing palladium on the surface of the substrate particles by immersion may be used.
  • Aspect 1 As an example of the production method of aspect 1, a method for producing conductive fine particles in which the crystallite diameter is 3 nm or less and the grain boundary structure of the nickel plating layer has a vein shape will be described.
  • a nickel layer is formed on the base particles carrying the noble metal as described above.
  • the nickel layer is extremely thinly formed to such an extent that the surface of the base particle carrying the noble metal is smooth, and the thickness of the nickel layer is adjusted by the second electroless plating.
  • the base particles are immersed in a plating solution in which a nickel salt, a reducing agent and a complexing agent are dissolved, so that the nickel ions in the plating solution are reduced with a reducing agent, starting from a noble metal catalyst. Then, nickel is deposited on the surface of the substrate particles to form a nickel layer.
  • first, base material particles are sufficiently dispersed in water to prepare an aqueous slurry of base material particles.
  • the base material particles are sufficiently dispersed in an aqueous medium for plating.
  • a conventionally known dispersing means such as a normal stirring device, a high-speed stirring device, a shearing dispersion device such as a colloid mill or a homogenizer may be employed.
  • a sound wave or a dispersant such as a surfactant
  • the aqueous slurry of the base material particles prepared above (or the base material particle dispersion after reduction treatment) is added to the electroless plating solution containing nickel salt, reducing agent, complexing agent and various additives. And then into an aqueous suspension.
  • the electroless plating reaction starts quickly when an aqueous slurry of the catalyzed substrate particles is added to the plating solution. Moreover, since this reaction is accompanied by the generation of hydrogen gas, the electroless plating reaction may be terminated when the generation of hydrogen gas is not completely recognized.
  • the nickel salt include nickel salts such as nickel chloride, nickel sulfate, and nickel acetate.
  • the reducing agent those exemplified in the catalytic treatment step can be used.
  • the plating solution used in the first electroless plating step uses an organic carboxylic acid such as citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, malonic acid or a salt thereof as a complexing agent. Of these, sodium tartrate is preferably used.
  • the concentration of the complexing agent is preferably 0.001 to 10 mol / L, more preferably 0.005 to 5 mol / L, and still more preferably 0.01 to 2 mol / L.
  • the nickel salt concentration in the plating solution used in the first electroless plating step is preferably 1.0 ⁇ 10 ⁇ 4 to 1.0 mol / L, more preferably 1.0 ⁇ 10 ⁇ 3 to 0.2 mol / L. It is.
  • the concentration of the reducing agent is preferably 1.0 ⁇ 10 ⁇ 4 to 3.0 mol / L, more preferably 1.0 ⁇ 10 ⁇ 3 to 0.3 mol / L.
  • the amount of the plating solution used is preferably 200 to 2,000,000 parts by mass, more preferably 500 to 1,000,000 parts per 100 parts by mass of the base particles carrying the noble metal. 000 parts by mass.
  • the liquid temperature and dipping time for immersing the substrate particles in the plating solution may be appropriately adjusted, but the liquid temperature is preferably 50 ° C. to 95 ° C.
  • a plating solution is added to the aqueous suspension after the first electroless plating step.
  • the plating solution used in the second electroless plating step is adjusted by dividing into two solutions of a nickel ion-containing solution containing a complexing agent and a reducing agent-containing solution. It is important that the nickel ion-containing liquid contains glycine as a complexing agent. In addition, it is important to provide a concentration gradient of the complexing agent in the plating solution by sequentially adding glycine to the complexing agent used in the first electroless plating step.
  • the concentration of the glycine is preferably 0.001 to 10 mol / L, more preferably 0.01 to 10 mol / L.
  • the nickel salt concentration in the plating solution used in the second electroless plating step is preferably 0.1 to 2 mol / L, more preferably 0.5 to 1.5 mol / L.
  • the concentration of the reducing agent is preferably 0.1 to 20 mol / L, more preferably 1 to 10 mol / L.
  • the ratio of glycine used in the second electroless plating step to the complexing agent used in the first electroless plating step in the plating solution is preferably 0.2 to 2, and particularly preferably 0.3 to 1.
  • the liquid temperature and dipping time for immersing the substrate particles in the plating solution may be appropriately adjusted, but the liquid temperature is preferably 50 ° C. to 95 ° C.
  • the manufacturing method of aspect 2 includes an electroless plating process performed using a specific plating solution.
  • Electroless Plating Step a conductive metal layer is formed on the surface of the catalyst base material particles on which the palladium catalyst is adsorbed in the catalyst step.
  • the electroless plating treatment by immersing the catalyzed substrate particles in a plating solution in which a reducing agent and a desired metal salt are dissolved, starting from a palladium catalyst, metal ions in the plating solution are reduced with a reducing agent, A desired metal is deposited on the surface of the substrate particles to form a conductive metal layer.
  • a plating solution in which a reducing agent and a desired metal salt are dissolved, starting from a palladium catalyst, metal ions in the plating solution are reduced with a reducing agent, A desired metal is deposited on the surface of the substrate particles to form a conductive metal layer.
  • a nickel layer having a crystallite diameter of 3 nm or less it is necessary to use a specific plating solution.
  • plating solutions examples include “Nimden (registered trademark) KFJ-20-M”, “Nimden KFJ-20-MA”, “Nimden NKY-2-M”, “Nimden” commercially available from Uemura Kogyo Co., Ltd. Nimden NKY-2-A ”,“ Nimden LPX-5M ”,“ Nimden LPX-A ”, and“ Schumer (registered trademark) S680 ”commercially available from Kanisen Corporation.
  • the conductive fine particles can be obtained by taking out the substrate particles on which the conductive metal layer is formed from the reaction system and washing and drying as necessary.
  • the crystallite diameter can be increased by subjecting the obtained conductive fine particles to heat treatment.
  • This technique is particularly effective when it is desired to control the crystallite diameter in the range of 1.5 nm to 3 nm (preferably 1.7 nm to 3 nm).
  • the heat treatment is performed on the conductive fine particles in a non-oxidizing atmosphere.
  • the non-oxidizing atmosphere include an inert atmosphere and a reducing atmosphere.
  • the inert atmosphere include an inert gas atmosphere such as nitrogen gas and argon gas.
  • the temperature of the heat treatment is 180 ° C. or higher, preferably 200 ° C. or higher, more preferably 230 ° C. or higher, further preferably 260 ° C. or higher, and particularly preferably 280 ° C. or higher.
  • the higher the heat treatment temperature the larger the crystallite diameter.
  • the heat treatment temperature is preferably 350 ° C. or less, more preferably 330 ° C. or less, and even more preferably 300 ° C. or less.
  • the heat treatment time is preferably 0.3 hours or more, more preferably 0.5 hours or more, and even more preferably 0.7 hours or more. The longer the heat treatment time, the larger the crystallite diameter.
  • the heat treatment time is preferably 10 hours or less, more preferably 5.0 hours or less, and even more preferably 3.0 hours or less.
  • the conductive fine particles may have a smooth surface or an uneven shape, but have a plurality of protrusions in that the binder resin can be effectively removed to connect to the electrode. Is preferred. By having the protrusion, connection reliability when the conductive fine particles are used for connection between the electrodes can be improved.
  • a method of forming protrusions on the surface of the conductive fine particles (1) after obtaining base particles having protrusions on the surface using a phase separation phenomenon of a polymer in a polymerization step in base particle synthesis A method of forming a conductive metal layer by electroless plating; (2) electroless after depositing inorganic particles such as metal particles and metal oxide particles or organic particles made of an organic polymer on the surface of the substrate particles; A method of forming a conductive metal layer by plating; (3) after performing electroless plating on the surface of the substrate particles, and attaching organic particles made of inorganic particles or organic polymers such as metal particles and metal oxide particles; (4) Utilizing the self-decomposition of the plating bath during the electroless plating reaction, depositing a metal that forms the core of the protrusion on the surface of the substrate particles, and further performing the electroless plating suddenly And the like; conductive metal layer containing section a method of forming a conductive metal layer became continuous film.
  • the height of the protrusion is preferably 20 nm to 1000 nm, more preferably 30 nm to 800 nm, still more preferably 40 nm to 600 nm, and particularly preferably 50 nm to 500 nm.
  • the height of the protrusion is determined by observing 10 arbitrary conductive fine particles with an electron microscope. Specifically, for the protrusions on the periphery of the conductive fine particles to be observed, the height of any ten protrusions per conductive fine particle is measured, and the measured value is obtained by arithmetic averaging.
  • the number of the protrusions is not particularly limited, but preferably has at least one protrusion on any orthographic projection surface when the surface of the conductive fine particles is observed with an electron microscope from the viewpoint of ensuring high connection reliability. , More preferably 5 or more, still more preferably 10 or more.
  • the conductive fine particle of the present invention may be in an embodiment having an insulating layer on at least a part of the surface (insulating coated conductive fine particle). If an insulating layer is further laminated on the conductive metal layer on the surface in this way, it is possible to prevent lateral conduction that is likely to occur when a high-density circuit is formed or when a terminal is connected.
  • the thickness of the insulating layer is preferably 0.005 ⁇ m to 1 ⁇ m, more preferably 0.01 ⁇ m to 0.8 ⁇ m. When the thickness of the insulating layer is within the above range, the electrical insulation between the particles becomes good while maintaining the conduction characteristics by the conductive fine particles.
  • the insulating layer is not particularly limited as long as the insulating property between the particles of the conductive fine particles can be ensured, and the insulating layer can be easily collapsed or peeled off by a certain pressure and / or heating.
  • polyethylene or the like Polyolefins; (meth) acrylate polymers and copolymers such as polymethyl (meth) acrylate; polystyrene; thermoplastic resins such as polystyrene; and cross-linked products thereof; thermosetting resins such as epoxy resins, phenol resins, melamine resins; Examples thereof include water-soluble resins such as alcohol and mixtures thereof; organic compounds such as silicone resins; and inorganic compounds such as silica and alumina.
  • thermoplastic resin and its crosslinked material it is preferable that it is a thermoplastic resin and its crosslinked material, and it is preferable that they are a (meth) acrylate polymer, a copolymer, and its crosslinked material.
  • a crosslinkable monomer is allowed to coexist during the formation of the (meth) acrylate polymer and copolymer, a crosslinked product of the polymer can be obtained.
  • the crosslinkable monomer is not particularly limited.
  • allyl (meth) acrylates such as allyl (meth) acrylate; ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, etc.
  • Alkanediol di (meth) acrylate Alkanediol di (meth) acrylate; diethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate etc. di (meth) acrylate etc. (Meth) acrylates; tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexa (meth) acrylate Hexa (meth) acrylates; aromatic hydrocarbon crosslinking agents such as divinylbenzene, divinylnaphthalene and derivatives thereof (preferably styrenic polyfunctional monomers such as divinylbenzene); N, N-divinylaniline, di Examples include heteroatom-containing crosslinking agents such as vinyl ether, divinyl sulfide
  • a preferable embodiment of the insulating coating layer is a crosslinked product of an aromatic hydrocarbon-based crosslinking agent of a thermoplastic resin, and a more preferable embodiment is a crosslinked product of a (meth) acrylate polymer and a copolymer by divinylbenzene. .
  • the insulating layer may be a single layer or a plurality of layers.
  • a single or a plurality of film-like layers may be formed, or a layer in which particles having insulating, granular, spherical, lump, scale or other shapes are attached to the surface of the conductive metal layer.
  • it may be a layer formed by chemically modifying the surface of the conductive metal layer, or a combination thereof.
  • insulating particles hereinafter referred to as “insulating particles” adhere to the surface of the conductive metal layer is preferable.
  • the average particle size of the insulating particles is appropriately selected depending on the average particle size of the conductive fine particles and the use of the insulating coated conductive fine particles.
  • the average particle size of the insulating particles is preferably in the range of 0.005 ⁇ m to 1 ⁇ m, and more Preferably, it is 0.01 ⁇ m to 0.8 ⁇ m.
  • the average particle diameter of the insulating particles is smaller than 0.005 ⁇ m, the conductive layers between the plurality of conductive fine particles are easily brought into contact with each other, and when the average particle diameter is larger than 1 ⁇ m, it is exhibited when the conductive fine particles are sandwiched between the opposing electrodes. There is a possibility that the electrical conductivity should be insufficient.
  • the coefficient of variation (CV value) in the average particle diameter of the insulating particles is preferably 40% or less, more preferably 30% or less, and most preferably 20% or less. If the CV value exceeds 40%, the conductivity may be insufficient.
  • the average particle diameter of the insulating particles is preferably 1/1000 or more and 1/5 or less of the average particle diameter of the conductive fine particles.
  • the insulating particle layer can be uniformly formed on the surface of the conductive fine particles. Two or more kinds of insulating particles having different particle diameters may be used.
  • the insulating particles may have a functional group on the surface in order to improve adhesion to the conductive fine particles.
  • Examples of the functional group include amino group, epoxy group, carboxyl group, phosphoric acid group, silanol group, ammonium group, sulfonic acid group, thiol group, nitro group, nitrile group, oxazoline group, pyrrolidone group, sulfonyl group, and hydroxyl group. Can be mentioned.
  • the coverage of the insulating particles on the surface of the conductive fine particles is preferably 1% to 98%, more preferably 5% to 95%.
  • the coverage of the conductive fine particles by the insulating particles is in the above range, it is possible to reliably insulate adjacent insulating coated conductive fine particles while ensuring sufficient electrical conductivity.
  • the coverage is determined by, for example, observing the surface of any 100 insulating coated conductive fine particles using an electron microscope, and the portion of the orthographic projection surface of the insulating coated conductive fine particles coated with the insulating particles and the resin. It can be evaluated by measuring the area ratio of the uncoated part of the particles.
  • Anisotropic Conductive Material The conductive fine particles of the present invention are useful as an anisotropic conductive material.
  • the anisotropic conductive material include those obtained by dispersing the conductive fine particles in a binder resin.
  • the form of the anisotropic conductive material is not particularly limited, and examples thereof include various forms such as an anisotropic conductive film, an anisotropic conductive paste, an anisotropic conductive adhesive, and an anisotropic conductive ink. By providing these anisotropic conductive materials between opposing substrates or between electrode terminals, good electrical connection can be achieved.
  • the anisotropic conductive material using the conductive fine particles of the present invention includes a conductive material for a liquid crystal display element (conductive spacer and composition thereof).
  • An anisotropic conductive material in the form of paste (anisotropic conductive paste) or film (anisotropic conductive film) in which conductive fine particles are dispersed in the binder resin is LCD (Liquid Crystal Display), PDP (PDP). Widely used as a material for bonding and electrically connecting FPD (Flat Panel Display) substrates such as Plasma Display Panel (OLED) and Organic Light-Emitting Diodes (OLED) to driver ICs that send image signals to this. .
  • PWB Printed Wiring Board
  • the anisotropic conductive material of the present invention is preferably used for FOG connection of FPD, COG connection, and touch panel lead-out circuit and FPC connection.
  • the anisotropic conductive material may be in the form of a paste or a film, but is preferably in the form of a film (anisotropic conductive film) in terms of further improving connection reliability.
  • the binder resin is not particularly limited as long as it is an insulating resin.
  • thermoplastic resins such as acrylic resin, styrene resin, ethylene-vinyl acetate resin, styrene-butadiene block copolymer; epoxy resin, phenol resin And thermosetting resins such as urea resin, polyester resin, urethane resin, and polyimide resin.
  • binder resin compositions fillers, softeners, accelerators, anti-aging agents, colorants (pigments, dyes), antioxidants, various coupling agents, light stabilizers, UV absorbers, lubricants as necessary. Further, an antistatic agent, a flame retardant, a heat conduction improver, an organic solvent, and the like can be blended.
  • the anisotropic conductive material can be obtained by dispersing conductive fine particles in the binder resin to obtain a desired form.
  • the binder resin and the conductive fine particles are separately used for connection.
  • the conductive fine particles may be present together with the binder resin between the base materials and between the electrode terminals.
  • the content of the conductive fine particles may be appropriately determined according to the use.
  • the volume is preferably 0.01% by volume or more, more preferably based on the total amount of the anisotropic conductive material. Is 0.03% by volume or more, more preferably 0.05% by volume or more, preferably 50% by volume or less, more preferably 30% by volume or less, and still more preferably 20% by volume or less. If the content of the conductive fine particles is too small, it may be difficult to obtain sufficient electrical continuity. On the other hand, if the content of the conductive fine particles is too large, the conductive fine particles are in contact with each other, and anisotropy is caused. The function as a conductive material may be difficult to be exhibited.
  • the coating thickness of the paste or adhesive, the printed film thickness, etc. considering the particle diameter of the conductive fine particles to be used and the specifications of the electrodes to be connected. It is preferable to set appropriately so that the conductive fine particles are held between the electrodes to be connected and the gap between the bonding substrates on which the electrodes to be connected are formed is sufficiently filled with the binder resin layer.
  • Evaluation method 1-1 Number average particle size, coefficient of variation (CV value) Measure the particle size of 30000 particles with a particle size distribution measuring device (“Coulter Multisizer III type”, manufactured by Beckman Coulter, Inc.) to obtain the average particle size based on the number and the standard deviation of the particle size. The CV value (coefficient of variation) based on the number of diameters was calculated.
  • Particle variation coefficient (%) 100 ⁇ (standard deviation of particle diameter / number-based average particle diameter)
  • a surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “Hytenol (registered trademark) N-08”
  • a dispersion liquid dispersed for 10 minutes was used as a measurement sample.
  • a dispersion obtained by hydrolysis and condensation reaction is diluted with a 1% aqueous solution of a surfactant (Daiichi Kogyo Seiyaku Co., Ltd., “Hytenol (registered trademark) N-08”). A sample was used.
  • a surfactant Daiichi Kogyo Seiyaku Co., Ltd., “Hytenol (registered trademark) N-08”.
  • Conductive metal layer cross-sectional observation 0.1 g of conductive fine particles were ground in an agate bowl and the metal layer was broken. The cross section in the thickness direction of the ground metal layer of the conductive metal layer was observed with a scanning electron microscope at a magnification of 100,000.
  • the structure of the nickel layer was evaluated as follows. A: The grain boundaries of the nickel layer are oriented in the thickness direction. B: No grain boundary is observed in the nickel layer. C: A structure in which the grain boundary of the nickel layer is both A and B is recognized. D: The grain boundary of the nickel layer forms a vein-like structure.
  • Phosphorus concentration 4 ml of aqua regia was added to 0.05 g of conductive fine particles, and the metal layer was dissolved and separated by stirring under heating. Thereafter, the contents of nickel and phosphorus in the filtrate were analyzed using an ICP emission analyzer.
  • Compression connection resistance value Measured at room temperature (25 ° C.) using a Shimadzu micro-compression tester (“MCT-W200” manufactured by Shimadzu Corporation) resistance measurement kit attachment device. Specifically, with respect to one sample particle spread on the sample stage, a constant loading speed (2.6 mN / second (0.27 gf / second)) toward the center of the particle using a circular plate indenter with a diameter of 50 ⁇ m. The measurement was performed with a load applied. The measurement was performed 10 times, and the respective average values of the resistance value (A) at 30% compression deformation and the resistance value (B) at 40% compression deformation of the particle diameter were obtained.
  • MCT-W200 Shimadzu micro-compression tester
  • the case where the 30% compression connection resistance value (A) was 80 ⁇ or less was evaluated as the initial resistance ⁇ , and the case where it was larger than 80 ⁇ was evaluated as the initial resistance ⁇ . Further, when B ( ⁇ ) / A ( ⁇ ) is 1.00 or less, the high compression resistance value is increased ⁇ , and when B ( ⁇ ) / A ( ⁇ ) is greater than 1.00 and less than 1.10, the high compression resistance value is increased. The case of less than 0.00 was evaluated as high compression resistance value increase x, and the case of 2.00 or more was evaluated as high compression resistance value increase xx.
  • An aqueous solution of dodecylbenzenesulfonic acid was added thereto as a curing catalyst, and condensation polymerization was carried out by maintaining at 50 to 60 ° C. for 3 hours to obtain an emulsion of a cured resin.
  • the paste obtained by precipitating and separating the cured resin from this emulsion was dispersed in Emulgen 430 and an aqueous dodecylbenzenesulfonic acid solution, kept at 90 ° C. for 1 hour, and then rapidly cooled.
  • a hardened spherical resin was obtained from the emulsion by sedimentation and separation (wherein the mass ratio of melamine / benzoguanamine / formaldehyde was 31.5 / 31.5 / 37).
  • HITENOL polyoxyethylene styrenated ammonium sulfate ester ammonium salt
  • DVB960 manufactured by Nippon Steel Chemical Co., Ltd., divinylbenzene content 96% by mass
  • 2,2′-azobis (2,4-dimethylvaleronitrile) (“Wako Pure Chemical Industries” “V -65 ”) 4.8 parts was added and emulsified and dispersed to prepare an emulsion of monomer components.
  • the resulting emulsion was added to the emulsion of the polysiloxane particles and further stirred.
  • the mixed liquid was sampled and observed with a microscope. As a result, it was confirmed that the polysiloxane particles were enlarged by absorbing the monomer.
  • Synthesis Example 4 Synthesis of Vinyl Polymer Particle 3
  • 1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 500 parts of methanol were added to a four-necked flask.
  • a vinyl polymer particle 3 was produced in the same manner as in Synthesis Example 1 except that a mixed solution of 100 parts of 3-methacryloxypropyltrimethoxysilane and 100 parts of methanol was added from the dropping port under stirring.
  • the number average particle diameter of the polysiloxane particles was 1.35 ⁇ m
  • the number average particle diameter of the vinyl polymer particles 3 was 2.71 ⁇ m
  • the coefficient of variation (CV value) was 3.4%.
  • Synthesis of vinyl polymer particles 4 In preparing an emulsion of polymerizable polysiloxane particles, 1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 550 parts of methanol were added to a four-necked flask. Then, a vinyl polymer particle 4 was produced in the same manner as in Synthesis Example 1 except that a mixed solution of 100 parts of 3-methacryloxypropyltrimethoxysilane and 50 parts of methanol was added from the dropping port under stirring. At this time, the number average particle size of the polysiloxane particles was 1.15 ⁇ m, the number average particle size of the vinyl polymer particles 4 was 2.30 ⁇ m, and the coefficient of variation (CV value) was 3.6%.
  • Synthesis of vinyl polymer particles 5 In preparing an emulsion of polymerizable polysiloxane particles, 1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 600 parts of methanol were added to a four-necked flask. A vinyl polymer particle 5 was prepared in the same manner as in Synthesis Example 1, except that 100 parts of 3-methacryloxypropyltrimethoxysilane was added from the dropping port under stirring and stirring. At this time, the number average particle diameter of the polysiloxane particles was 0.99 ⁇ m, the number average particle diameter of the vinyl polymer particles 5 was 2.02 ⁇ m, and the coefficient of variation (CV value) was 3.8%.
  • Conductive fine particles 1 were obtained by using amino resin particles as base particles and subjecting them to the following plating steps (catalyzing treatment step, plating film forming step).
  • the obtained conductive fine particles 1 had a number average particle diameter of 14.2 ⁇ m, the nickel layer had a film thickness of 120 nm and a phosphorus concentration of 8.9% by mass.
  • the cross section in the thickness direction of the nickel layer of the obtained conductive fine particles was observed with a scanning electron microscope at a magnification of 100000 times, grain boundaries were observed, and the orientation direction was oriented in a vein pattern obliquely to the thickness.
  • Catalytic treatment step 40 mL of water was added to 3 g of the above base particle, and ultrasonic dispersion was performed. While stirring this dispersion at a liquid temperature of 60 ° C., 0.2 mL of palladium chloride aqueous solution (concentration: 19.5 g / L) was added and maintained for 5 minutes to activate palladium ions on the surface of the base particles. Processed. Next, the base particles were separated by filtration and washed with 70 mL of hot water at 70 ° C., and then 20 mL of water was added to prepare a slurry.
  • Electroless plating step The slurry after the reduction treatment obtained in the catalytic treatment step was heated to 75 ° C. with a plating solution (sodium tartrate concentration 16.9 g / L, nickel sulfate concentration 1.33 g / L, hypochlorous acid) Sodium phosphate concentration 1.85 g / L) was added to 180 mL with stirring. One minute after adding the slurry, 0.37 g of sodium hypophosphite was added, and stirring was continued for another minute.
  • a plating solution sodium tartrate concentration 16.9 g / L, nickel sulfate concentration 1.33 g / L, hypochlorous acid
  • the nickel ion-containing liquid (glycine concentration 40.5 g / L, nickel sulfate concentration 133.2 g / L), reducing agent-containing liquid (sodium hypophosphite) were added to the mixed liquid of the slurry and plating solution obtained above.
  • the liquid temperature was maintained at 75 ° C., and stirring was continued for 60 minutes after the generation of hydrogen gas was completed. Thereafter, solid-liquid separation was performed, and the particles were washed with ion-exchanged water and methanol, and then dried with a vacuum dryer at 100 ° C. Thereby, the electroconductive fine particles 1 which gave nickel plating were obtained.
  • the vinyl polymer particles 1 are subjected to etching treatment with sodium hydroxide, then sensitized by contact with a tin dichloride solution, and then activated by immersion in a palladium dichloride solution. Formed. After adding 10 parts of base particles having palladium nuclei to 900 parts of ion-exchanged water and carrying out ultrasonic dispersion treatment, “Nimden (registered trademark) KFJ-20-M” (Uemura) was used as the electroless plating solution. 500 parts of Kogyo Co., Ltd. and 225 parts of “Nimden KFJ-20-MA” (Uemura Kogyo Co., Ltd.) were added and heated to 70 ° C.
  • the pH of the plating solution before the plating reaction was 4.55. After confirming that the generation of hydrogen gas was completed while maintaining the liquid temperature at 70 ° C., the mixture was stirred for 30 minutes, solid-liquid separation was performed, and ion-exchanged water and methanol were washed in this order, and then at 100 ° C. Vacuum-dried for 2 hours to obtain conductive fine particles 2 plated with nickel.
  • the obtained conductive fine particles 2 had a number average particle size of 6.3 ⁇ m, the nickel layer had a thickness of 130 nm and a phosphorus concentration of 12.7% by mass.
  • the pH of the plating solution before the plating reaction was 4.64. After confirming that the generation of hydrogen gas was completed while maintaining the liquid temperature at 70 ° C., the mixture was stirred for 30 minutes, solid-liquid separation was performed, and ion-exchanged water and methanol were washed in this order, and then at 100 ° C. Vacuum-dried for 2 hours to obtain conductive fine particles 3 plated with nickel.
  • the obtained conductive fine particles 3 had a number average particle size of 6.3 ⁇ m, the nickel layer had a thickness of 160 nm and a phosphorus concentration of 12.4% by mass.
  • Production Example 4 Similarly to Production Example 1, conductive fine particles 4 were obtained in the same manner as Production Example 1 except that amino resin particles were used as substrate particles and the raw materials, conditions, etc. in the plating step were changed.
  • the obtained conductive fine particles 4 had a number average particle diameter of 14.3 ⁇ m, the nickel layer had a thickness of 160 nm and a phosphorus concentration of 9.8% by mass.
  • the conductive fine particles were heat-treated at 280 ° C. for 2 hours in a nitrogen (inert) atmosphere to obtain conductive fine particles 5 subjected to nickel plating.
  • the obtained conductive fine particles 5 had a number average particle size of 6.2 ⁇ m, the nickel layer had a thickness of 80 nm, and a phosphorus concentration of 9.5% by mass.
  • the pH of the plating solution before the plating reaction was 6.33. After confirming that the generation of hydrogen gas was completed while maintaining the liquid temperature at 70 ° C., the mixture was stirred for 30 minutes, solid-liquid separation was performed, and ion-exchanged water and methanol were washed in this order, and then at 100 ° C. Vacuum-dried for 2 hours to obtain conductive fine particles 6 plated with nickel.
  • the obtained conductive fine particles had a number average particle size of 6.4 ⁇ m, the nickel layer had a thickness of 190 nm and a phosphorus concentration of 7.4% by mass.
  • Production Example 7 In the same manner as in Production Example 1, amino resin particles were used as substrate particles, and the raw materials, conditions, etc. in the plating step were changed to obtain conductive fine particles 7.
  • the obtained conductive fine particles 7 had a number average particle size of 14.3 ⁇ m, the nickel layer had a thickness of 160 nm and a phosphorus concentration of 8.0% by mass.
  • Production Example 8 The vinyl polymer particles 1 were etched with sodium hydroxide and then sensitized by contact with a tin dichloride solution, and then immersed in a palladium dichloride solution to form palladium nuclei. After adding 10 parts of base particles with palladium nuclei to 900 parts of ion-exchanged water and carrying out ultrasonic dispersion treatment, “Nimden KLP-1-MM” (Uemura Kogyo Co., Ltd.) was used as the electroless plating solution. 750 parts and “Nimden KLP-1-MA” (Uemura Kogyo Co., Ltd.) 300 parts were added and heated to 70 ° C. to cause electroless nickel plating reaction.
  • the pH of the plating solution before the plating reaction was 6.27. After confirming that the generation of hydrogen gas was completed while maintaining the liquid temperature at 70 ° C., the mixture was stirred for 30 minutes, solid-liquid separation was performed, and ion-exchanged water and methanol were washed in this order, and then at 100 ° C. Vacuum-dried for 2 hours to obtain conductive fine particles 8 plated with nickel.
  • the obtained conductive fine particles 8 had a number average particle size of 6.4 ⁇ m, the nickel layer had a thickness of 160 nm and a phosphorus concentration of 2.8% by mass.
  • Production Example 9 Conductive fine particles 9 are produced in the same manner as in Production Example 5 except that the vinyl polymer particles 2 are used as base particles and the amount of the electroless nickel plating solution is adjusted so that the thickness of the nickel layer is 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 3.3 ⁇ m.
  • Production Example 10 The conductive fine particles 10 were prepared in the same manner as in Production Example 5 except that the vinyl polymer particles 3 were used as base particles and the amount of electroless nickel plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 3.0 ⁇ m.
  • Production Example 11 Conductive fine particles 11 were obtained in the same manner as in Production Example 2 except that the vinyl polymer particles 3 were used as base particles. The number average particle diameter of the obtained conductive fine particles was 3.0 ⁇ m.
  • Production Example 12 Conductive fine particles 12 are produced in the same manner as in Production Example 5 except that the vinyl polymer particles 4 are used as base particles and the amount of the electroless nickel plating solution is adjusted so that the thickness of the nickel layer is 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 2.6 ⁇ m.
  • Production Example 13 Conductive fine particles 13 are produced in the same manner as in Production Example 5 except that the vinyl polymer particles 5 are used as base particles and the amount of the electroless nickel plating solution is adjusted so that the thickness of the nickel layer is 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 2.3 ⁇ m.
  • Production Example 14 The conductive fine particles 14 were prepared in the same manner as in Production Example 5 except that the vinyl polymer particles 6 were used as base particles and the amount of electroless nickel plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 2.6 ⁇ m.
  • Production Example 15 Conductive fine particles 15 were produced in the same manner as in Production Example 5 except that vinyl polymer particles 7 were used as base particles and the amount of electroless nickel plating solution was adjusted so that the nickel layer had a thickness of 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 2.6 ⁇ m.
  • Production Example 16 Conductive fine particles 16 are produced in the same manner as in Production Example 5 except that vinyl polymer particles 8 are used as base particles and the amount of electroless nickel plating solution is adjusted so that the thickness of the nickel layer is 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 2.6 ⁇ m.
  • Production Example 17 Conductive fine particles 17 were prepared in the same manner as in Production Example 8 except that the vinyl polymer particles 2 were used as base particles and the total amount of electroless plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 3.3 ⁇ m.
  • Production Example 18 Conductive fine particles 18 were prepared in the same manner as in Production Example 8 except that the vinyl polymer particles 4 were used as base particles and the total amount of electroless plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 2.6 ⁇ m.
  • Production Example 19 Conductive fine particles 19 were produced in the same manner as in Production Example 8 except that the vinyl polymer particles 5 were used as base particles and the total amount of electroless plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 2.3 ⁇ m.
  • Production Example 20 Conductive fine particles 20 were produced in the same manner as in Production Example 5 except that vinyl polymer particles 9 were used as base particles and the amount of electroless nickel plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 10.3 ⁇ m.
  • Production Example 21 The conductive fine particles 21 were produced in the same manner as in Production Example 5 except that the vinyl polymer particles 10 were used as base particles and the amount of electroless nickel plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 20.3 ⁇ m.
  • Production Example 22 Conductive fine particles 22 were produced in the same manner as in Production Example 8 except that the vinyl polymer particles 10 were used as base particles and the amount of electroless nickel plating solution was adjusted so that the thickness of the nickel layer was 150 nm. Got. The number average particle diameter of the obtained conductive fine particles was 20.4 ⁇ m.
  • the particle size of the resin particles (1) in this dispersion was measured with a dynamic light scattering particle size distribution measuring device (“NICOMP380” manufactured by PS Japan). The volume average particle size was 158 nm, and the variation coefficient was 11%. Met.
  • the resin particle dispersion (1) was diluted with deionized water so that the particle concentration was 5.0% by mass. To 100 parts of the obtained resin particle dispersion, 12 and 50 parts of the conductive fine particles obtained in Production Example 12 were added and dispersed uniformly, and then water was distilled off with an evaporator to remove the surface of the conductive fine particles. Insulating coated conductive fine particles (1) coated with resin particles were obtained.
  • Production Example 25 Insulating coated conductive fine particles (2) were obtained in the same manner as in Production Example 24 except that the conductive fine particles 18 obtained in Production Example 18 were used.
  • anisotropic conductive material for insulation characteristic evaluation 20 parts of insulating coated conductive fine particles (1), 65 parts of epoxy resin (“YL980” manufactured by Japan Epoxy Resin Co., Ltd.) as a binder resin, epoxy curing agent (“NOVACURE (produced by Asahi Kasei Corporation) (Registered trademark) HX3941HP ”) 35 parts and 200 parts of 1 mm ⁇ zirconia beads were mixed and subjected to bead mill dispersion for 30 minutes to obtain an anisotropic conductive adhesive (1) as an anisotropic conductive material.
  • a conductive connection structure was prepared using the obtained anisotropic conductive adhesive, and the following evaluation was performed.
  • the conductive connection structure is manufactured by first anisotropically bonding the release film (polyethylene terephthalate film having a release treatment on one side with a silicone resin) to a release treatment surface of 25 ⁇ m.
  • the adhesive layer was formed by apply
  • the release film is peeled from the obtained anisotropic conductive sheet, and only the adhesive layer is placed between two ITO-attached glass substrates on which an ITO transparent electrode film having a 150 ⁇ m wide pattern is formed on the inner surface.
  • the conductive connection structure was obtained by heating and pressing at 1 MPa and 185 ° C. for 15 seconds. Conductive connection structures were obtained in the same manner for the conductive fine particles 12 and 18 and the insulating coated conductive fine particles (2).
  • Table 1 shows the results of X-ray diffraction analysis and compression deformation characteristic evaluation of the conductive fine particles obtained in Production Examples 1 to 8.
  • the crystallite diameter of the nickel layer is 3 nm or less.
  • L1 is large. That is, it can be seen that when the crystallite diameter of the nickel layer is 3 nm, the nickel layer is more flexible and hard to break. This is because the conductive fine particles having a crystallite size of 3 nm in the nickel layer have higher adhesion to the base material particles, and it is easier to show deformation behavior linked to the deformation behavior of the base material particles during compression deformation. it is conceivable that.
  • connection resistance value is lower when the crystallite diameter of the nickel layer is 3 nm or less and the nickel layer is more flexible. Further, the effect of suppressing the resistance value when the crystallite diameter is 3 nm or less is further clarified at the time of high compression. In particular, the smaller the particle diameter, the more pronounced the effect of suppressing the resistance value. ( Figure 2)
  • amino resin particles are used as base particles.
  • the conductive fine particles of Production Example 4 having a crystallite diameter of 3 nm or less had an initial resistance of 65 ⁇ and a low electric resistance value, but the conductive fine particles of Production Example 7 having a crystallite diameter of 5.85 nm were used.
  • the initial resistance was 191 ⁇ , and the electrical resistance value was remarkably increased. Therefore, even when relatively hard amino resin particles having a 10% K value of 6775 N / mm 2 are used, the flexibility improvement effect of the nickel layer by setting the crystallite diameter to 3 nm or less, and further the electric resistance value It can be seen that a reduction effect of can be obtained.
  • Production Example 23 was conductive fine particles having protrusions, and both the 30% compression connection resistance value and the 40% compression connection resistance value were low, and the resistance value during high compression was effectively suppressed.
  • the conductive fine particles having protrusions are used as an anisotropic conductive material, the binder resin is eliminated by the protrusions, and the protrusions easily bite into the substrate, so that the connection reliability can be further improved.
  • the base particle is soft (for example, 6000 N / mm 2 or less)
  • the effect of improving the flexibility of the nickel layer by setting the crystallite diameter to 3 nm or less It can be seen that the effect of reducing the electrical resistance value becomes even more remarkable.
  • the 10% K value was as soft as 2891 N / mm 2
  • the 30% compression resistance value increased to 198 ⁇ in the conductive fine particles of Production Example 22 having a crystallite diameter of 8.64 nm.
  • the conductive fine particles of the present invention are suitable for anisotropic conductive materials such as conductive spacers for LCD, anisotropic conductive films, anisotropic conductive pastes, anisotropic conductive adhesives, anisotropic conductive inks, etc. Used.

Abstract

La présente invention vise à fournir une couche métallique électro-conductrice comportant une couche de nickel possédant une flexibilité améliorée. À cet effet, la présente invention concerne des particules fines électro-conductrices comportant des particules de base et une couche métallique électro-conductrice avec laquelle la surface des particules de base a été revêtue, et sont caractérisées en ce que la couche métallique électro-conductrice comporte une couche de nickel, le nickel ayant un diamètre des cristallites de direction [111], tel que déterminé par la diffractométrie des rayons X, égal ou inférieur à 3nm.
PCT/JP2012/074293 2011-09-22 2012-09-21 Particules fines électro-conductrices et matériau conducteur anisotrope en contenant WO2013042785A1 (fr)

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JP2016027558A (ja) * 2014-06-24 2016-02-18 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
JP2017188482A (ja) * 2012-12-31 2017-10-12 株式会社ドクサンハイメタル タッチスクリーンパネル用導電粒子、およびこれを含む導電材料
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US11020825B2 (en) 2015-11-20 2021-06-01 Sekisui Chemical Co., Ltd. Connecting material and connection structure
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US11017916B2 (en) 2015-11-20 2021-05-25 Sekisui Chemical Co., Ltd. Particles, connecting material and connection structure
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