WO2010035708A1 - 金属皮膜形成方法及び導電性粒子 - Google Patents

金属皮膜形成方法及び導電性粒子 Download PDF

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WO2010035708A1
WO2010035708A1 PCT/JP2009/066366 JP2009066366W WO2010035708A1 WO 2010035708 A1 WO2010035708 A1 WO 2010035708A1 JP 2009066366 W JP2009066366 W JP 2009066366W WO 2010035708 A1 WO2010035708 A1 WO 2010035708A1
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conductive particles
metal
metal film
silver
particles
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PCT/JP2009/066366
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English (en)
French (fr)
Japanese (ja)
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英克 黒田
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宇部日東化成 株式会社
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Priority to KR1020167029352A priority Critical patent/KR20160137589A/ko
Priority to JP2010530833A priority patent/JP5422563B2/ja
Priority to CN200980131789.1A priority patent/CN102124142B/zh
Publication of WO2010035708A1 publication Critical patent/WO2010035708A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

  • the present invention relates to a conductive film that can be used as, for example, a conductive material, an electromagnetic shielding material, and a metal film forming method for forming a metal film on non-conductive particles.
  • Electroless plating is known as a technique for forming a metal film on non-conductive particles.
  • a pretreatment for depositing a catalyst for starting the electroless plating is performed on the surface of the non-conductive particles.
  • non-conductive particles are brought into contact with an aqueous solution of stannous chloride and then brought into contact with an aqueous solution of palladium chloride.
  • the palladium colloid is adsorbed on the surface of the nonconductive particles by the reducing action of the tin ions adsorbed on the surface of the nonconductive particles.
  • the palladium colloid acts as a catalyst that initiates electroless plating.
  • the electroless plating bath contains a metal salt, a metal complexing agent, a pH adjusting agent, a reducing agent and the like.
  • Patent Document 1 proposes the use of a metal plating powder having a uniform and strong covering power.
  • This metal plating powder is obtained by a catalytic step for supporting noble metal ions on the surface of the core material, and then an electroless plating treatment for electroless plating on the core material.
  • the catalyzing step after the noble metal ions are captured by the organic or inorganic core material, the noble metal ions are reduced and supported on the surface of the core material.
  • the electroless plating constituent liquid is divided into at least two liquids having different components, and then they are added separately and simultaneously.
  • displacement plating is known as a technique for forming a noble metal film on non-conductive particles (see Patent Documents 2 and 3).
  • As a general replacement plating there is a method in which electroless nickel plating is formed as a base layer, and the base layer is replaced with a noble metal.
  • electroless nickel plating sodium hypophosphite monohydrate, citric acid and the like are usually added to the plating solution in order to properly adjust the pH of the plating solution.
  • cobalt is added to the plating solution to a concentration of several hundred ppm in order to control the crystal structure of the noble metal film.
  • the metal film produced by displacement plating includes nickel having a higher electrical resistance value than silver and gold, phosphorus, cobalt, and the like as impurities.
  • Gold and silver are listed as noble metals with high conductivity. Silver has a higher conductivity and is cheaper than gold. For this reason, the utility value of the electroconductive particle which formed the metal membrane
  • the metal film is formed of at least two layers of a nickel layer and a silver layer. As described above, the metal film composed of a plurality of layers is disadvantageous in terms of cost because the amount of metal used is increased and waste liquid treatment is required.
  • the present inventor has found a technique capable of forming a silver film on a micron-sized non-conductive particle without applying a base plating.
  • An object of the present invention is to provide a metal film forming method capable of forming a silver film even when the particle size of non-conductive particles is extremely small.
  • Another object of the present invention is to provide conductive particles having excellent conductivity and low cost even if the particle size of the non-conductive particles is extremely small.
  • a metal film forming method for forming a metal film on the surface of non-conductive particles by electroless plating.
  • the electroless plating is performed after a pretreatment for attaching metal nuclei to the surface of non-conductive particles, and forms a metal film made of silver in the presence of a hydrophilic polymer having a pyrrolidone group.
  • a dispersion in which non-conductive particles are dispersed in an aqueous solution of a hydrophilic polymer having a pyrrolidone group, and then start electroless plating in the dispersion.
  • the hydrophilic polymer having a pyrrolidone group preferably contains at least polyvinylpyrrolidone.
  • the electroless plating is preferably performed by a silver mirror reaction.
  • the pretreatment is such that the treatment liquid containing the silane coupling agent, the hydrolysis catalyst and the metal salt is brought into contact with the non-conductive particles, and then the metal of the metal salt is precipitated by the reducing agent. Therefore, it is preferable that the silane coupling agent has a functional group that forms a chelate with respect to the metal of the metal salt.
  • the metal of the metal core is preferably gold or silver.
  • conductive particles imparted with conductivity by a metal film formed on the entire surface of the non-conductive particles are provided.
  • the metal film consists only of a silver film.
  • the conductive fine particles it is preferable that only gold and silver elements are detected as elements other than the elements contained in the nonconductive particles in the fluorescent X-ray analysis of the conductive particles.
  • the number ratio of particles having an electrical resistance value of 10 ⁇ or less after 240 hours in an environment of a temperature of 60 ° C. and a humidity of 90% RH is preferably 80% or more.
  • the number ratio of particles having an uncoated portion of a silver film is preferably 10% or less.
  • the conductive fine particles are preferably used as a sealing agent for liquid crystal display elements.
  • the conductive fine particles are preferably used as an anisotropic conductive material.
  • a method for producing conductive particles formed by forming a metal film on the surface of nonconductive particles by electroless plating is performed after a pretreatment for attaching metal nuclei to the surface of non-conductive particles, and forms a metal film made of silver in the presence of a hydrophilic polymer having a pyrrolidone group.
  • conductive particles obtained by forming a metal film on the surface of non-conductive particles.
  • the metal film is formed by electroless plating that is performed after pretreatment to attach metal nuclei to the surface of non-conductive particles and forms a metal film made of silver in the presence of a hydrophilic polymer having a pyrrolidone group. Is done.
  • the metal film consists only of a silver film.
  • the particle size of the non-conductive particles is extremely small, it is possible to provide conductive particles that easily exhibit excellent conductivity and are low in cost.
  • FIG. 2 is a scanning electron micrograph showing silica particles used in Example 1.
  • FIG. The scanning electron micrograph which shows the nonelectroconductive particle which performed the pre-processing in Example 1.
  • FIG. 2 is a scanning electron micrograph showing conductive particles of Example 1.
  • FIG. 2 is a chart of fluorescent X-ray analysis showing detection of silver for the conductive particles of Example 1.
  • FIG. 3 is a chart of fluorescent X-ray analysis showing gold detection for the conductive particles of Example 1.
  • FIG. The scanning electron micrograph which shows the electroconductive particle of Example 1 after a wet heat test.
  • the optical microscope photograph which shows the dispersion state in resin about the electroconductive particle of Example 1.
  • FIG. 4 is a scanning electron micrograph showing conductive particles of Comparative Example 1.
  • FIG. 6 is a scanning electron micrograph showing conductive particles of Comparative Example 2. The optical micrograph which shows the dispersion state in resin about the electroconductive particle of the comparative example 2.
  • FIG. 6 is a scanning electron micrograph showing conductive particles of Comparative Example 3. The scanning electron micrograph which shows the electroconductive particle of the comparative example 3 after a wet heat test.
  • the metal film forming method of this embodiment is a method of forming a metal film on non-conductive particles by electroless plating.
  • the electroless plating is performed after a pretreatment for attaching metal nuclei to non-conductive particles, and forms a metal film made of silver in the presence of a hydrophilic polymer having a pyrrolidone group.
  • the nonconductive particles will be described.
  • the non-conductive particles are configured as a base material that forms a metal film.
  • the material of the nonconductive particles include at least one selected from silica, ceramics, glass, and resins.
  • silica include completely crystallized dry silica (cristobalite) and water-dispersed silica (colloidal silica).
  • ceramics include alumina, sapphire, mullite, titania, silicon carbide, silicon nitride, aluminum nitride, zirconia, and the like.
  • the glass include various shot glasses such as BK7, SF11, and LaSFN9, optical crown glass, soda glass, low expansion borosilicate glass, and the like.
  • the non-conductive particles are preferably at least one selected from silica, ceramics, and glass, more preferably silica, from the viewpoint of small variation in particle size.
  • the shape of the non-conductive particles include a spherical shape, a rod shape, a plate shape, a needle shape, and a hollow shape.
  • the shape of the non-conductive particles is preferably spherical considering the dispersibility of the non-conductive particles or the dispersibility of the obtained conductive particles.
  • the particle size of the non-conductive particles is not particularly limited, but is preferably 0.5 to 100 ⁇ m, more preferably 0.5 to 10 ⁇ m, and still more preferably 1 to 5 ⁇ m.
  • the particle size of the non-conductive particles is measured from a photograph of a scanning electron microscope.
  • the CV value obtained by the following formula is preferably 10% or less, and more preferably 5% or less.
  • CV value (%) ⁇ [standard deviation of particle diameter ( ⁇ m)] / [average particle diameter ( ⁇ m)] ⁇ ⁇ 100
  • pretreatment for attaching metal nuclei to non-conductive particles is performed. Next, this preprocessing will be described.
  • metal nuclei are attached to the non-conductive particles.
  • the metal nucleus acts so that the metal film made of silver adheres to the non-conductive particles.
  • the metal core is preferably made of gold or silver. A metal nucleus made of gold or silver hardly forms an adverse effect on the conductivity of silver that becomes a metal film, and can form a metal film stably.
  • a treatment liquid containing a silane coupling agent, a hydrolysis catalyst, and a gold salt is brought into contact with non-conductive particles, and then metal ions are deposited by depositing metal ions with a reducing agent. Is preferred. Thereby, formation of the metal film by electroless plating proceeds uniformly.
  • the silane coupling agent has a hydrolyzable functional group that generates a silanol group by hydrolysis.
  • the hydrolyzable functional group include an alkoxy (—OR) group directly bonded to a Si atom.
  • R constituting the alkoxy group is preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.
  • the silane coupling agent used in the metal film forming method of the present embodiment has a functional group that forms a chelate with respect to the metal of the metal salt.
  • the functional group that forms a chelate with respect to the metal of the metal salt include a polar group and a hydrophilic group. Specifically, a functional group having at least one atom selected from nitrogen atom, sulfur atom and oxygen atom is preferable.
  • the functional group include at least one functional group selected from the group consisting of —SH, —CN, —NH 2 , —SO 2 OH, —SOOH, —OPO (OH) 2 , and —COOH. .
  • the functional group may form a salt.
  • the salt includes alkali metal salts such as sodium, potassium, lithium, Or ammonium salt etc. are mentioned.
  • alkali metal salts such as sodium, potassium, lithium, Or ammonium salt etc. are mentioned.
  • a basic group such as —NH 2
  • examples of the salt include inorganic acid salts such as hydrochloric acid, sulfuric acid and nitric acid, and organic acid salts such as formic acid, acetic acid, propionic acid and trifluoroacetic acid.
  • silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl). ) -3-aminopropyltriethoxysilane and the like. From the viewpoints of the cost of the silane coupling agent and ease of handling, 3-aminopropyltrimethoxysilane is particularly preferable.
  • the hydrolysis catalyst accelerates hydrolysis of the hydrolyzable functional group of the silane coupling agent.
  • the hydrolysis catalyst include organic acids such as acetic anhydride, glacial acetic acid, propionic acid, citric acid, formic acid and oxalic acid, aluminum chelate compounds such as aluminum alkyl acetate, and inorganic alkaline compounds such as aqueous ammonia. It can.
  • organic acids such as acetic anhydride, glacial acetic acid, propionic acid, citric acid, formic acid and oxalic acid
  • aluminum chelate compounds such as aluminum alkyl acetate
  • inorganic alkaline compounds such as aqueous ammonia.
  • the amount of the hydrolysis catalyst used per mole of the silane coupling agent is preferably 0.5 to 5.0 moles, and more preferably 1.5 to 2.5 moles.
  • the amount of the metal salt used per mole of the silane coupling agent is preferably 0.005 to 0.05 mole, and more preferably 0.015 to 0.025 mole.
  • the amount of the reducing agent used relative to 1 mol of the metal salt is preferably 0.025 to 0.25 mol, and more preferably 0.075 to 0.125 mol.
  • the solvent or dispersion medium constituting the treatment liquid for pretreatment water or an aqueous solvent can be mentioned.
  • the aqueous solvent is a mixed solvent of water and an organic solvent.
  • the organic solvent include lower alcohols such as methanol, ethanol, propanol and butanol, and ketones such as acetone. These organic solvents may be used alone or in combination of two or more. Next, electroless plating will be described.
  • Electroless plating a known electroless plating method using a metal salt, a reducing agent, or the like can be applied.
  • the reducing agent include borohydrides such as sodium tetrahydroborate (alkali metal borohydrides such as sodium borohydride, ammonium borohydrides), hydrazine compounds, hypochlorite, and the like.
  • An inorganic reducing agent such as an acid salt or an organic reducing agent such as formaldehyde, acetaldehyde, citric acid, or sodium citrate can be used. These reducing agents may be used alone or in combination of two or more.
  • the temperature conditions and reaction time of electroless plating are set according to the conventional method of electroless plating.
  • the amount of the reducing agent used relative to 1 mol of the metal salt is preferably 0.025 to 0.25 mol, and more preferably 0.075 to 0.125 mol.
  • the electroless plating it is preferable to use a silver mirror reaction from the viewpoints of excellent reaction stability and reducing impurities as much as possible. That is, the substance involved in the silver mirror reaction is easily removed from the metal film by washing. For this reason, an extremely high-purity metal film can be formed.
  • silver is precipitated by reducing a silver ammine complex with a reducing agent. Specifically, a reducing agent such as formalin is added to an aqueous ammonia solution of silver nitrate. Thereby, silver is deposited on the surface of the non-conductive particles based on the metal nucleus.
  • Electroless plating forms a metal film made of silver in the presence of a hydrophilic polymer having a pyrrolidone group. According to this film formation, a silver film can be continuously formed on the nonconductive particles subjected to the pretreatment.
  • hydrophilic polymers having a pyrrolidone group include polyvinylpyrrolidone (PVP), poly (N-vinyl-2-pyrrolidone-g-citric acid), and poly (N-vinyl-2-pyrrolidone-co-itaconic acid). And poly (N-vinyl-2-pyrrolidone-co-styrene). These hydrophilic polymers may be used alone or in combination of two or more.
  • the hydrophilic polymer having a pyrrolidone group has a nitrogen atom and an oxygen atom in its side chain. For this reason, the hydrophilic polymer having a pyrrolidone group is coordinated to a metal nucleus adhering to the non-conductive particles or silver deposited by electroless plating.
  • the hydrophilic polymer coordinated in this way allows the formation of a metal film uniformly when silver deposits around the metal core to form a film, and the adhesion of the metal film to non-conductive particles. It is presumed to increase the nature. As a result, a highly uniform and uniform metal film is formed with non-conductive particles.
  • Polyvinyl alcohol (PVA) which is a kind of hydrophilic polymer, has an oxygen atom in the side chain in contrast to the hydrophilic polymer having a pyrrolidone group.
  • PVA Polyvinyl alcohol
  • a continuous metal film is not formed on the surface of the nonconductive particles. From this, it is presumed that at least nitrogen atoms act on the formation of a continuous metal film. Further, it is presumed that the presence of oxygen atoms and nitrogen atoms as a pyrrolidone skeleton has an advantageous effect in the growth of silver based on metal nuclei adsorbed on non-conductive particles and the formation of a continuous film.
  • the hydrophilic polymer having a pyrrolidone group preferably contains at least polyvinylpyrrolidone.
  • polyvinylpyrrolidone which is a homopolymer, is more easily coordinated with precipitated silver than a copolymer having a pyrrolidone group in the side chain. Thereby, the silver film is more stably formed.
  • polyvinylpyrrolidone is easily coordinated to the metal nucleus in the non-conductive particles having gold or silver attached as the metal nucleus. Therefore, the silver film is more stably formed.
  • the electroless plating of this embodiment is started in a dispersion after preparing a dispersion in which non-conductive particles are dispersed in an aqueous solution of a hydrophilic polymer having a pyrrolidone group.
  • a hydrophilic polymer having a pyrrolidone group is uniformly and sufficiently coordinated with the metal nucleus adsorbed on the non-conductive particles. That is, when electroless plating is started in the dispersion, a hydrophilic polymer having a pyrrolidone group acts sufficiently, so that a silver film is more stably formed.
  • the dispersion medium for dispersing the non-conductive particles is an aqueous dispersion medium.
  • the aqueous dispersion medium is water or a mixed liquid of water and an organic solvent, and also serves as a solvent for a hydrophilic polymer having a pyrrolidone group.
  • the organic solvent has compatibility with water. Examples of the organic solvent include lower alcohols such as methanol, ethanol, propanol and butanol, and ketones such as acetone. These organic solvents may be used alone or in combination of two or more.
  • the hydrophilic polymer having a pyrrolidone group is classified according to the K value obtained by the Fikencher method.
  • the K value is a value serving as a reference for the molecular weight of a hydrophilic polymer having a pyrrolidone group.
  • a lower K value means a smaller molecular weight of the hydrophilic polymer. That is, it means that the higher the K value, the higher the thickening effect of the dispersion. Further, the thickening effect also depends on the concentration of the hydrophilic polymer in the dispersion medium.
  • the K value and concentration of the hydrophilic polymer having a pyrrolidone group are preferably 30 to 120 and a concentration of 0.5 to 10%, more preferably 90 to 90%. -120, and the concentration is 2.0-5.0%.
  • the K value of the hydrophilic polymer is less than 30 and the concentration is less than 0.5%, the flow of the nonconductive fine particles may not be effectively suppressed.
  • the K value of the hydrophilic polymer exceeds 120 and the concentration exceeds 10%, the viscosity of the dispersion is excessively increased, so that the precipitated silver may not easily come into contact with the non-conductive particles. As a result, the formation of the metal film may be delayed or the silver particles may aggregate in the dispersion.
  • the concentration (C) of the hydrophilic polymer having a pyrrolidone group in the dispersion is represented by the following formula as the concentration with respect to the aqueous dispersion medium.
  • Concentration (C) [%] ⁇ [Hydrophilic polymer (g)] / [Aqueous dispersion medium (ml)] ⁇ ⁇ 100
  • the hydrophilic polymer having a pyrrolidone group protects the surface of the conductive particles by coordinating with the silver film. That is, the hydrophilic polymer having a pyrrolidone group relaxes the cohesive force of silver constituting the metal film. Thereby, the electroconductive particle formed in the dispersion liquid becomes difficult to aggregate each other.
  • the obtained conductive particles are separated from the dispersion, washed, and then dried to obtain conductive particle powder (conductive powder). Since the aggregation of the conductive powder is suppressed, the particle size distribution of the conductive powder is narrow.
  • the CV value in the conductive powder is preferably 10% or less, and more preferably 5% or less.
  • the stirring method in the electroless plating is not particularly limited, for example, stirring by a general stirring device such as a stirring blade, a magnetic stirrer, etc., in addition to the dispersing means, simultaneously with stirring by the stirring device, Alternatively, stirring by ultrasonic irradiation alone, a method using a dispersing means, and the like can be mentioned.
  • the conductive particles are given conductivity by a metal film formed on the entire surface of the non-conductive particles.
  • the metal film consists only of a silver film. That is, the conductive particles do not have a plating layer that serves as an underlayer for the silver film.
  • the metal film consists of an aggregate of continuous silver fine particles.
  • the metal film is composed of a continuous film in which silver fine particles are densely arranged.
  • An aggregate of continuous silver fine particles refers to an aggregate of silver fine particles that are densely arranged to such a level that a discontinuous metal film cannot be confirmed when the metal film is observed with a scanning microscope at a magnification of 5000 to 10,000 times. It means the body.
  • the thickness of the metal film is preferably 50 nm or more from the viewpoint of exhibiting stable conductivity.
  • the conductive particles having the metal film impurities can be extremely reduced.
  • the purity of the conductive particles can be confirmed by fluorescent X-ray analysis.
  • FIG. 3 is an electron micrograph showing an example of the conductive powder. From FIG. 3, it is confirmed that the continuous silver film has a petal shape. On the other hand, in conventional conductive particles in which a silver film is formed without using a hydrophilic polymer having a pyrrolidone group, the uncoated portion of the film forms a crater shape.
  • the conductive particles of the present embodiment are a conductive particle group such as a conductive powder, a conductive particle dispersion, or the like, there are no conductive particles having an uncoated portion of the silver film, or It is characterized by very little, if any. In the case of the conductive particle group, the number ratio of particles having an uncoated portion of the silver film can be suppressed to 10% or less.
  • carbon is detected as an element other than the elements contained in the nonconductive particles in the total organic carbon analysis.
  • nitrogen is detected as an element other than the elements contained in the nonconductive particles in the Kjeldahl method.
  • Carbon and nitrogen detected in the conductive particles are derived from a hydrophilic polymer having a pyrrolidone group.
  • the conductive particles can be suitably used, for example, as various anisotropic conductive materials in addition to a sealing agent for liquid crystal display elements.
  • liquid crystal display panels have been required to be small in size and fast in response. Therefore, it is desired to reduce the width of the frame region where the seal portion of the liquid crystal display panel is arranged, and to narrow the gap between the active matrix substrate and the counter substrate. Therefore, in particular, it is required to reduce the particle size of the conductive particles used for the seal portion of the liquid crystal display panel.
  • the conductive particles of the present embodiment can meet the above-described demand by being applied to, for example, a seal portion of a liquid crystal display panel as particles of 5 ⁇ m or less, for example.
  • the conductive particles of the present embodiment can exhibit stable electrical characteristics even in a high-temperature and high-humidity environment when used for sealing agents for liquid crystal display elements, anisotropic conductive materials, and the like.
  • 240 hours have passed in an environment of a temperature of 60 ° C. and a humidity of 90% RH when the conductive particles are a conductive powder, a conductive particle dispersion, or the like.
  • the number ratio of particles having a subsequent electrical resistance value of 10 ⁇ or less can be 80% or more.
  • the electroless plating in the metal film forming method is performed after a pretreatment for attaching metal nuclei to non-conductive particles, and a metal film made of silver in the presence of a hydrophilic polymer having a pyrrolidone group.
  • a silver film can be formed without providing a plating layer as an underlayer even for non-conductive particles having a particle size of 5 ⁇ m or less.
  • the aggregated particles can be removed by classification after the formation of the metal film, there is a possibility that productivity may be reduced.
  • the metal film forming method of the present embodiment since a metal film made of silver is formed in the presence of a hydrophilic polymer having a pyrrolidone group, aggregation of non-conductive fine particles is suppressed. As a result, a powder of conductive particles having excellent dispersibility can be obtained.
  • a method for forming a metal film that can easily form a silver film even when the particle size of the non-conductive particles is extremely small is provided.
  • electroless plating is started in the dispersion. Thereby, the metal film which consists of silver can be formed more stably.
  • the hydrophilic polymer having a pyrrolidone group contains at least polyvinylpyrrolidone. Thereby, the metal film which consists of silver can be formed more stably.
  • Electroless plating is performed by a silver mirror reaction. Thereby, impurities contained in the conductive particles can be reduced as much as possible.
  • the metal of the metal salt is precipitated by the reducing agent. It is preferable to attach metal nuclei. Thereby, since a metal nucleus adheres more uniformly, the uniformity of a metal membrane
  • the metal of the metal core is gold or silver. Thereby, it does not have a bad influence on the electroconductivity of silver used as a metal film. Moreover, a metal film can also be formed stably. (7) The metal film of the conductive particles consists only of a silver film. For this reason, the electroconductive particle excellent in electroconductivity can be provided. Further, the cost is lower than that of a metal film composed only of a gold film.
  • the number ratio of particles having an electrical resistance value of 10 ⁇ or less after elapse of 240 hours in an environment of temperature 60 ° C. and humidity 90% RH is 80% or more. Thereby, the reliability of electrical characteristics can be improved.
  • the number ratio of the particles having an uncoated portion of the silver film is 10% or less. Thereby, the reliability of electrical characteristics can be improved.
  • the conductive particles are preferably used as, for example, a sealing agent or an anisotropic conductive material for a liquid crystal display element due to its stable conductivity and excellent electrical characteristics.
  • the conductive particles of the present embodiment are configured without using nickel plating as an underlayer. For this reason, it is excellent in corrosion resistance under high temperature and high humidity conditions.
  • the non-conductive particles are composed of at least one selected from silica, ceramics, and glass. Stability can be improved. Therefore, the practicality of the conductive particles can be improved.
  • the embodiment may be modified as follows.
  • electroless plating is started in the dispersion.
  • a hydrophilic polymer aqueous solution may be gradually added to the electroless plating solution to form a metal film.
  • the metal core to be adhered in the pretreatment may be formed from a metal other than gold or silver.
  • a metal other than gold or silver noble metals such as platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir) are preferable.
  • the metal film may be formed by performing electroless plating in multiple stages. That is, the metal film may be composed of a multilayer film made of silver.
  • the particle size of the conductive particles is not particularly limited, but is preferably in the range of 0.5 to 5 ⁇ m.
  • Example 1 Pretreatment In a 500 mL Erlenmeyer flask, 10 g of silica particles (average particle size: 2.4 ⁇ m, CV value: 1.36%, particle size of 70 particles measured from scanning electron micrograph) was added, and isopropyl alcohol was added. (IPA) 65 ml was added and sonicated for 10 minutes. Next, 65 ml of methanol was added and stirred with a magnetic stirrer for 10 minutes, 37 ml of 25% aqueous ammonia solution was added, and the mixture was stirred for 60 minutes in an oil bath at 30 ° C. (this solution is referred to as solution A).
  • solution A this solution is referred to as solution A).
  • solution C sodium tetrahydroborate
  • B liquid sodium tetrahydroborate
  • 3 hours the oil bath was heated to 65 ° C. and stirred for 3 hours. Stirring was stopped and methanol classification was performed three times, and then suction filtration was performed to collect silica particles on which metal nuclei were formed, followed by drying in an oven at 80 ° C. for 24 hours. The obtained powder of particles was red.
  • FIG. 1 shows a scanning electron micrograph of silica particles.
  • FIG. 2 shows a scanning electron micrograph of silica particles in which metal nuclei are formed.
  • FIG. 2 shows that the ultrafine gold particles are uniformly attached to the entire surface of the silica particles.
  • the average particle diameter of 70 particles was measured from a scanning electron micrograph, and the CV value indicating the extent of the particle size distribution was determined. The results are shown in Table 1.
  • FIG. 3 A scanning electron micrograph of the conductive particles is shown in FIG. Referring to FIG. 3, it can be seen that a metal film is formed on the entire surface of the particles.
  • the average particle diameter of 70 particles was measured from a scanning electron micrograph and the CV value was determined. The results are shown in Table 2.
  • the thickness of the metal film was 0.14 ⁇ m. As a result of observing the number of particles having a crater-like uncoated portion with the micrograph shown in FIG. 3, it was 0/100, and the number ratio of the particles was 0%.
  • Example 1 The electroconductive particles obtained in Example 1 were subjected to a wet heat test under the conditions of 60 ° C., 90% RH, and 240 h using a thermo-hygrostat (manufactured by Espec Corp.). A scanning electron micrograph of the conductive particles after the wet heat test is shown in FIG. As is clear from FIGS. 3 and 6, no change was observed in the state of the metal film before and after the wet heat test.
  • Example 1 In the conductive particles before and after the wet heat test, the difference in the number of measurable electric resistance values was one. The number ratio of particles having an electric resistance value of 10 ⁇ or less was 86%. This result shows that the electroconductive particle obtained in Example 1 has sufficient heat-and-moisture resistance.
  • Comparative Example 1 a metal film was formed without blending polyvinyl pyrrolidone.
  • Comparative Example 1 first, 475 mL of water was added to 10 g of the particles obtained in the same manner as “(A) pretreatment” in Example 1 and subjected to ultrasonic treatment for 10 minutes, and then 28.65 g of silver nitrate was added to magnetically. Stir with a stirrer for 10 minutes.
  • FIG. 8 shows a scanning electron micrograph of the conductive particles on which the metal film is formed.
  • the conductive particles of Comparative Example 1 no metal film was formed on a part of the surface.
  • the number of particles having a crater-like uncoated portion with the micrograph shown in FIG. 8 it was 53/100, and the number ratio of the particles was 53%.
  • Comparative Example 2 polyvinyl pyrrolidone was changed to polyvinyl alcohol.
  • Comparative Example 2 first, 475 mL of water was added to 10 g of the particles obtained in the same manner as in “(A) pretreatment” of Example 1, and ultrasonic treatment was performed for 10 minutes, and then 28.65 g of silver nitrate was added to magnetically. Stir with a stirrer for 10 minutes. Next, 28 g of polyvinyl alcohol (degree of polymerization: 400 to 600) was added, and the mixture was further stirred for 60 minutes, and then irradiated with ultrasonic waves for 15 minutes.
  • FIG. 9 shows a scanning electron micrograph of the conductive particles on which the metal film is formed.
  • the conductive particles of Comparative Example 2 no metal film was formed on a part of the surface.
  • Comparative Example 3 In Comparative Example 3, a conductive particle powder was prepared in which substitution gold plating for forming electroless nickel plating as an underlayer on resin particles was performed. A scanning electron micrograph of the conductive particles on which the metal film is formed is shown in FIG. As is clear from FIG. 11, in the conductive particles of Comparative Example 3, no metal film was formed on a part of the surface. As a result of measuring the number of particles having a crater-like uncoated portion with the micrograph shown in FIG. 11, it was 57/100, and the number ratio of the particles was 57%.
  • the difference in the number of measurable electric resistance values is 39, the expression rate after the wet heat test is only 10% (5/50 particles), and the electric resistance value The number ratio of particles having a particle size of 10 ⁇ or less was 6%. From this result, it was confirmed that the electroconductive particle obtained in the comparative example 3 was inferior in heat-and-moisture resistance.
  • Comparative Example 4 The polyvinyl pyrrolidone in Comparative Example 1 was changed to polyethylene glycol (molecular weight about 20,000).
  • Comparative Example 4 first, 475 mL of water was added to 10 g of the particles obtained in the same manner as in “(A) pretreatment” in Example 1, and ultrasonic treatment was performed for 10 minutes, and then 28.65 g of silver nitrate was added to magnetically. Stir with a stirrer for 10 minutes. Next, 28 g of polyethylene glycol was added and the mixture was further stirred for 60 minutes, and then irradiated with ultrasonic waves for 15 minutes.
  • Dispersibility evaluation in resin Dispersibility evaluation of the conductive particles obtained in Comparative Example 4 in the resin was performed in the same manner as the conductive particles of Example 1. As a result of observation with an optical microscope, 8 or more coalesced particles were observed, and it was confirmed that the dispersibility in the resin was inferior to that of the conductive particles obtained in Example 1.

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JP2014074191A (ja) * 2012-10-02 2014-04-24 Kanto Gakuin 無電解めっき方法及び無電解めっき膜
WO2016121558A1 (ja) * 2015-01-28 2016-08-04 三菱マテリアル株式会社 銀被覆粒子及びその製造方法
JP2016146319A (ja) * 2015-01-28 2016-08-12 三菱マテリアル株式会社 銀被覆粒子及びその製造方法
KR20240033287A (ko) 2021-08-02 2024-03-12 니폰 가가쿠 고교 가부시키가이샤 도전성 입자, 그 제조 방법 및 도전성 재료

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JP6328575B2 (ja) * 2015-02-23 2018-05-23 東京エレクトロン株式会社 触媒層形成方法、触媒層形成システムおよび記憶媒体
CN105177538B (zh) * 2015-09-16 2018-11-23 东莞深圳清华大学研究院创新中心 一种纳米铜包覆单晶蓝宝石纤维的制备方法
CN111386580B (zh) * 2017-12-22 2022-04-22 埃卡特有限公司 导电粒子、组合物、制品和制造导电粒子的方法
KR102113732B1 (ko) * 2019-03-21 2020-05-21 주식회사 아이에스시 도전성 분말 및 이를 포함하는 검사용 커넥터

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JP2013249403A (ja) * 2012-06-01 2013-12-12 Asahi Kasei Chemicals Corp 複合粒子及びこれを含有する粒子分散液
JP2014074191A (ja) * 2012-10-02 2014-04-24 Kanto Gakuin 無電解めっき方法及び無電解めっき膜
WO2016121558A1 (ja) * 2015-01-28 2016-08-04 三菱マテリアル株式会社 銀被覆粒子及びその製造方法
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