WO2013085039A1 - Conductive fine particles and anisotropically conductive material containing same - Google Patents
Conductive fine particles and anisotropically conductive material containing same Download PDFInfo
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- WO2013085039A1 WO2013085039A1 PCT/JP2012/081809 JP2012081809W WO2013085039A1 WO 2013085039 A1 WO2013085039 A1 WO 2013085039A1 JP 2012081809 W JP2012081809 W JP 2012081809W WO 2013085039 A1 WO2013085039 A1 WO 2013085039A1
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- fine particles
- conductive fine
- conductive
- nickel
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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
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 heat and moisture resistance.
- 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.
- the application range of electronic devices varies, and for example, use in high temperature and high humidity environments may be required. It may be desired to improve the wet heat resistance of the conductive fine particles, that is, to suppress an increase in electric resistance value at high temperature and high humidity in accordance with such applications.
- the conductive fine particles are not sufficiently heat and heat resistant, and no improvement method is known.
- Patent Document 1 by controlling the crystallite diameter of the buffer layer formed on the surface of the base material particles in the conductive particles, it is possible to suppress cracking and peeling of the surface conductive layer when the conductive particles are pressed. It is disclosed. However, Patent Document 1 does not teach at all about the relationship between the crystalline state of the conductive particles and the heat and humidity resistance.
- An object of the present invention is to obtain conductive fine particles having excellent heat and moisture resistance. More specifically, an object is to provide anisotropic conductive connections, that is, conductive fine particles having stable connection resistance under wet heat conditions in a compressed state.
- the conductive fine particles according to the present invention are composed of base particles and a conductive metal layer covering the surface of the base particles, and the conductive metal layer includes a nickel layer, and the conductive fine particles When X-ray powder diffraction measurement is performed, diffraction lines belonging to the lattice plane (200) of nickel are observed.
- the substrate particles are preferably vinyl polymer particles, and the number average particle diameter of the substrate particles is preferably 1 ⁇ m or more and 50 ⁇ m or less.
- 10% K value of the base particle is 100 N / mm 2 or more, it is preferable that 40000N / mm 2 or less.
- the number average particle diameter of the base particles is 3 ⁇ m or less and the 10% K value is more than 4000 N / mm 2
- the number average particle diameter of the base particles is 3 ⁇ m or less
- d (200) / d (111)) is 0.2 or more aspects
- the 10% K value of the base particle is 100 N / mm 2 or more, even aspects is 4000 N / mm 2 or less, a preferred embodiment of the present invention, respectively is there.
- the present invention also includes an anisotropic conductive material containing the fine particles.
- the crystal of the nickel layer grows in the direction perpendicular to the (200) plane (that is, [200] direction), the wet heat resistance of the conductive fine particles can be improved. As a result, anisotropic conductive connection with excellent connection stability is possible.
- 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 powder X-ray diffraction measurement is performed, diffraction lines belonging to the nickel lattice plane (200) are observed, that is, a direction perpendicular to the nickel lattice plane (200) ([ 200] direction). Thereby, the wet heat resistance of the conductive fine particles can be improved.
- the crystallite diameter in the direction perpendicular to the (200) plane (hereinafter, the crystallite diameter in the direction perpendicular to the (xyz) plane is expressed as d (xyz)) is preferably 0.5 nm or more.
- the lower limit of d (200) is more preferably 0.8 nm or more, and further preferably 1 nm or more.
- the upper limit of d (200) is not particularly limited, but is preferably 10 nm or less, more preferably 6 nm or less, and further preferably 5 nm or less.
- d (200) / d (111) is preferably 0.05 or more, more preferably 0.2 or more, further preferably 0.20 or more (particularly more than 0.20), and further preferably 0. .35 or more. It can be said that the larger these values are, the clearer the existence of diffraction lines attributed to the (200) plane.
- d (200) / d (111) satisfies the above range when the number average particle diameter of the conductive fine particles is 3 ⁇ m or less, the heat and moisture resistance can be maintained for a longer time.
- d (200) / d (111) is preferably less than 1, for example, more preferably 0.9 or less, and most preferably 0.8 or less.
- d (111) is usually less than 10 nm, preferably more than 2.0 nm.
- crystallite diameters such as d (200) and d (111) referred to in the present invention are values calculated using the Scherrer equation from the diffraction line width (half width) obtained by powder X-ray diffraction measurement, A specific method for measuring the crystallite diameter will be described in Examples.
- 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—Cu, Ni—P, Ni—B, Ni—Zn, Ni—Sn, Ni—W, and Ni—. Co, Ni—Ti and the like are preferable, and among these, a Ni—P alloy is preferable.
- the P (phosphorus) concentration in the Ni—P alloy is preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 10% by mass or less.
- the P concentration is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more.
- the P concentration is the ratio of P mass to the total mass of Ni and P in the nickel alloy (P / (P + Ni)).
- the thickness of the nickel layer is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, more preferably 0.07 ⁇ m or more.
- the thickness of the nickel layer is preferably 0.3 ⁇ m or less, more preferably 0.25 ⁇ m or less, still more preferably 0.2 ⁇ m or less, and still more preferably 0.12 ⁇ 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 the dispersion stability when dispersed in a binder or the like is improved.
- the conductive metal layer may be laminated with another conductive metal layer or may not be laminated, but is preferably not laminated.
- the nickel layer becomes the outermost layer of the conductive metal layer.
- the metal constituting the other conductive metal layer is not particularly limited. 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 conductive metal layer include 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. When laminating another conductive metal layer, the other conductive metal layer may be the outermost layer.
- a preferred form of the conductive metal layer is a form in which the metal element constituting the other conductive metal layer such as gold or palladium forms a metal layer (including an alloyed layer) mixed with the nickel element. one of.
- the nickel layer when gold plating is performed after the nickel layer is formed, at least a part of nickel atoms constituting the nickel layer is replaced with gold, so that the conductive metal layer is formed as described above.
- 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 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 thickness of the conductive metal layer is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and further preferably 0.07 ⁇ m or more. 0.3 ⁇ m or less is preferable, more preferably 0.25 ⁇ m or less, still more preferably 0.2 ⁇ m or less, and still more preferably 0.12 ⁇ m or less.
- thickness of the conductive metal layer 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 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 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, polychlorinated Polyolefins such as vinyl, polytetrafluoroethylene, polyisobutylene, and polybutadiene; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonates; polyamides; polyimides; phenol formaldehyde resin; These resins may be used alone or in combination of two or more.
- 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-butanediol di (meth) acrylate, etc.), polyalkylene glycol di (meth) acrylate (for example, diethylene glycol di (meth)) Acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol Rudi (meth) acryl
- (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.
- aromatic hydrocarbon crosslinking agents especially styrene polyfunctional monomers
- (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 preferred.
- alkanediol di (meth) acrylate and polyalkylene glycol di (meth) acrylate are preferable, and ethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate are more preferable.
- 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 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 2000 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 600 parts by mass or less, and particularly preferably 500 parts by mass or less.
- 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, for example, 20% by mass or more is preferable, more preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 70% by mass or more. The more the crosslinkable monomer, the harder the vinyl polymer particles. If the ratio of the crosslinkable monomer is within the above range, the restoring force is improved while maintaining excellent elastic deformation characteristics. Can be made.
- 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. Therefore, a high pressure may be required. Therefore, the ratio of the crosslinkable monomer is, for example, 98% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
- 10% K value of a base particle can be made small, so that the ratio of a crosslinkable monomer is small, for example, can also be 4000 N / mm ⁇ 2 > or less.
- the proportion of the crosslinkable monomer is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less. is there.
- 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 constituting the amino resin particles is 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 preferably contains 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 of the amino resin particles is sharper, and the particle diameter 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.
- Organopolysiloxane Particles Organopolysiloxane Particles
- Organopolysiloxane particles are composed of one or more silane monomers (silane crosslinkable monomers, silane noncrosslinkable monomers) that do not contain vinyl groups. It is obtained by decomposing and condensing.
- 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.
- the number average particle diameter of the substrate particles (resin particles) is preferably 1.0 ⁇ m or more, more preferably 1.1 ⁇ m or more, still more preferably 1.2 ⁇ m or more, still more preferably 1.3 ⁇ m or more, and 50 ⁇ m or less. Is preferable, more preferably 30 ⁇ m or less, and still more preferably 10 ⁇ m or less.
- the number-based variation coefficient (CV value) of the particle diameter of the substrate particles is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 5.0% or less, and still more preferably 4. 5% or less, particularly preferably 4.0% or less.
- the number average particle diameter of the base particles is preferably less than 10.0 ⁇ m, more preferably 3.0 ⁇ m or less, still more preferably 2.8 ⁇ m or less, still more preferably less than 2.8 ⁇ m, even more.
- it is 2.7 ⁇ m or less, still more preferably 2.6 ⁇ m or less, particularly preferably 2.5 ⁇ m or less, while 1.0 ⁇ m or more is preferable, and 1.5 ⁇ m or more is more preferable.
- the base particles among the vinyl polymer particles, amino resin particles, and organopolysiloxane particles, vinyl polymer particles formed by polymerizing a monomer component containing a crosslinkable monomer, Moreover, organopolysiloxane particles using trialkoxysilane as a silane-based crosslinkable monomer are preferred. Vinyl polymer particles formed by polymerizing a monomer component containing a crosslinkable monomer are more preferable in that the 10% K value can be easily controlled.
- the proportion of the crosslinkable monomer (total of vinyl-based crosslinkable monomer and silane-based crosslinkable monomer) in the total monomers constituting the fine vinyl polymer particles is preferably 30% by mass or more.
- the number average particle diameter of the base particles (resin particles) is a relatively large particle diameter in the range of 1.0 ⁇ m or more and 50 ⁇ m or less.
- it is preferably 6 ⁇ m or more, more preferably 7 ⁇ m or more, and still more preferably 8 ⁇ m or more.
- an upper limit is 25 micrometers or less, for example, More preferably, it is 23 micrometers or less, More preferably, it is 20 micrometers or less.
- 10% K value of the base material particles 100 N / mm 2 or more, it is preferable that 40000N / mm 2 or less.
- the lower limit of the 10% K value of the base particle when used as an anisotropic conductive material, the surrounding binder can be more sufficiently eliminated, the biting into the electrode can be improved, and the connection resistance The value can be further improved.
- setting the upper limit of the 10% K value of the base particles also contributes to ensuring a better electrical contact state.
- the 10% K value is more preferably 500 N / mm 2 or more, particularly 1000 N / mm 2 or more. Further, the 10% K value is more preferably 27000 N / mm 2 or less, particularly 15000 N / mm 2 or less.
- the base particles are softer.
- 10% K value of the base particle is 100 N / mm 2 or more and 4000 N / mm 2 or less.
- the 10% K value of the substrate particles is within the above range, the time during which the heat and humidity resistance can be exhibited becomes longer. That is, it can be seen that the use of soft base particles having a small 10% K value can suppress the increase in resistance value under a moist heat condition for a longer time. It is considered that during compression, the load is dispersed in the base particles and the load on the nickel layer is dispersed.
- the 10% K value of the base particles is more preferably 300 N / mm 2 or more, further preferably 700 N / mm 2 or more, and particularly preferably 1000 N / mm 2 or more. is there. Further, it is more preferably 3900 N / mm 2 or less, further preferably 3850 N / mm 2 or less, particularly preferably 3800 N / mm 2 or less.
- This effect does not depend on the particle diameter of the base particles, but such soft base particles are particularly useful because the number average particle diameter of the base particles is, for example, 6 ⁇ m or more, more preferably 7 ⁇ m or more, More preferably, the thickness is 8 ⁇ m or more. An upper limit becomes like this.
- the polymer particles are preferably vinyl polymer particles formed by polymerizing a monomer component containing a crosslinkable monomer.
- the proportion of the crosslinkable monomer (total of the vinyl-based crosslinkable monomer and the silane-based crosslinkable monomer) in the total monomers constituting the soft vinyl polymer particles is preferably 50% by mass or less. More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
- the non-crosslinkable monomer contained in the monomer component constituting the soft vinyl polymer particles includes a styrene monofunctional monomer and alkyl (meth) acrylates as preferred non-crosslinkable monomers. It is preferable. Of the styrenic monofunctional monomers, styrene is preferred.
- alkyl (meth) acrylates methyl (meth) acrylate and alkyl (meth) acrylate having an alkyl group with 3 or more carbon atoms are preferable, and the 10% K value can be adjusted to a predetermined range.
- the alkyl (meth) acrylate whose carbon number of an alkyl group is 3 or more is more preferable, and a butyl (meth) acrylate is especially preferable.
- the total proportion of preferred monomers (styrene monofunctional monomers and alkyl (meth) acrylates) in the total amount of non-crosslinkable monomers is preferably 50% by mass or more.
- the upper limit or lower limit of the 10% K value of the base particles may be adjusted according to the particle diameter of the base particles. By adjusting according to the particle diameter, the control effect of 10% K value can be more reliably exhibited.
- the 10% K value is preferably 3000 N / mm 2 or more. More preferably, it is 3500 N / mm 2 or more, more preferably more than 4000 N / mm 2 . Further, it is preferably 40000N / mm 2 or less, more preferably 30000 N / mm 2, more preferably not more than 25000N / mm 2.
- 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 conductive fine particles is preferably 1.0 ⁇ m or more, more preferably 1.1 ⁇ m or more, still more preferably 1.2 ⁇ m or more, still more preferably 1.3 ⁇ m or more, and particularly preferably 1. It is 4 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 10 ⁇ m or less.
- the number-based variation coefficient (CV value) of the conductive fine particles is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 5.0% or less, and still more preferably 4%. .5% or less, particularly preferably 4.0% or less.
- the number average particle diameter is preferably less than 10.0 ⁇ m, more preferably 3.2 ⁇ m or less, still more preferably 3.0 ⁇ m or less, even more preferably, for the reason that the effects of the present invention become more remarkable.
- 2.8 ⁇ m or less even more preferably 2.7 ⁇ m or less, even more preferably 2.6 ⁇ m or less, while 1.1 ⁇ m or more is preferable and 1.6 ⁇ m or more is more preferable.
- the base particles are soft, the crystal of the nickel layer grows in the [200] direction as described above, so that the increase in the connection resistance value of the conductive fine particles can be more effectively suppressed even under wet and heat conditions.
- the soft base particles are particularly useful when the number average particle diameter of the conductive fine particles is, for example, 6.3 ⁇ m or more, more preferably 7.3 ⁇ m or more, and further preferably 8.3 ⁇ m or more.
- An upper limit is 25 micrometers or less, for example, More preferably, it is 23 micrometers or less, More preferably, it is 20 micrometers 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 conductive fine particles of the present invention include conductive spacers for LCD, conductive fine particles for anisotropic conductive connection in the mounting of semiconductors and electronic circuits, anisotropic conductive films, anisotropic conductive pastes, anisotropic conductive adhesives, It can be suitably used for anisotropic conductive materials such as anisotropic conductive ink.
- the conductive fine particles can be produced by an electroless plating method.
- a special treatment in the electroless plating step is performed. Is required. That is, it is important that the plating solution (nickel salt-containing plating solution) in the electroless plating step contains glycine and sodium acetate, in other words, glycine and sodium acetate coexist during nickel plating.
- the mass ratio of sodium acetate to glycine is 1.8 or less (preferably 1.7 or less, more preferably 1.6 or less), or (ii) acetic acid to glycine
- the mass ratio of sodium exceeds 1.8 (preferably 1.9 or more, more preferably 2.0 or more)
- 270 ° C. or more preferably 275
- the conductive fine particles of the present invention can be obtained by heat treatment at a temperature of not lower than ° C., more preferably not lower than 280 ° C.
- the lower limit of the mass ratio of sodium acetate to glycine is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 1.0 or more.
- the upper limit of the mass ratio of sodium acetate to glycine is preferably 3 or less, more preferably 2.5 or less.
- the heat treatment temperature in an inert atmosphere is preferably 350 ° C. or lower, more preferably 320 ° C. or lower, and further preferably 300 ° C. or lower.
- the lower limit of the heat treatment time under an inert atmosphere is preferably 0.1 hour or more, more preferably 1 hour or more, and the upper limit of the heat treatment time is preferably 20 hours or less, more preferably 10 hours or less, Preferably it is 5 hours or less.
- the conductive metal layer is formed by a normal method other than the above specific treatment.
- the base particles subjected to the electroless plating step are usually subjected to a catalyst treatment prior to the plating 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., imparting hydrophilicity to the surface of the substrate particles, and increasing the wettability to the subsequent electroless plating solution. In addition, minute unevenness is formed, and the adhesion between the substrate particles after electroless plating 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 palladium ions (Pd 2+ ) is added.
- a method of depositing palladium on the surface of the substrate particles by immersion (sensitizing-activating method) may be used.
- the liquid temperature and the immersion time when the substrate particles are immersed in the solution containing tin ions (Sn 2+ ) or the solution containing palladium ions (Pd 2+ ) are sufficient for each ion in the substrate particles.
- the liquid temperature is preferably 10 to 60 ° C.
- the immersion time is preferably 1 minute to 120 minutes, for example.
- Electroless Plating Step a normal electroless plating step is employed except that the above-described specific treatment (combination of glycine and sodium acetate and the presence or absence of heat treatment according to these ratios) is performed. That is, in the electroless plating step, first, the catalyst base material particles are sufficiently dispersed in water to prepare an aqueous slurry of the catalyst base material particles. Here, in order to develop stable conductive properties, it is preferable to sufficiently disperse the catalyzed base particles in an aqueous medium for plating.
- an untreated surface (a surface on which no conductive metal layer is present) is formed on the contact surface between the base material particles.
- means for dispersing the catalyzed substrate particles in the aqueous medium include 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, and ultrasonic waves and a dispersing agent (interface).
- An activator or the like may be used.
- an electroless plating reaction is caused by adding the aqueous slurry of the catalyzed substrate particles prepared above to an electroless plating solution containing a nickel salt, a reducing agent, a complexing agent and various additives.
- the electroless plating reaction starts quickly when an aqueous slurry of catalyzed substrate particles is added. Moreover, since this reaction is accompanied by the generation of hydrogen gas, the electroless plating reaction may be terminated when hydrogen gas generation is no longer observed.
- the conductive 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.
- nickel salt contained in the electroless plating solution examples include nickel chloride, sulfate, acetate, and the like. That is, nickel salts such as nickel chloride, nickel sulfate, and nickel acetate may be contained in the electroless plating solution. Only 1 type may be sufficient as electroconductive metal salt, and 2 or more types may be sufficient as it. The concentration of the nickel salt may be appropriately determined in consideration of the size (surface area) of the base particles so that a conductive metal layer having a desired film thickness is formed.
- Examples of the reducing agent contained in the electroless plating solution include formaldehyde, sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, potassium tetrahydroborate, glyoxylic acid, hydrazine, and the like. . Only one reducing agent may be used, or two or more reducing agents may be used.
- complexing agent As a complexing agent, the above glycine acts as it. Therefore, in the present invention, the use of other complexing agents is not essential, but other complexing agents may be used as necessary.
- Other complexing agents include citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, gluconic acid or carboxylic acids (salts) such as alkali metal salts and ammonium salts thereof; amino acids such as glutamic acid; ethylenediamine, alkylamine, etc. Aminic acid; other ammonium, EDTA, pyrophosphoric acid (salt); and the like.
- the concentration of glycine is, for example, about 20 to 50 g per 1 L of plating solution, and the concentration of complexing agent is, for example, about 20 to 150 g per 1 L of plating solution.
- the pH of the electroless plating solution is not limited, but is preferably 6 to 14. Further, the temperature of the electroless plating solution is not particularly limited, but is, for example, 30 to 100 ° C.
- the electroless plating process may be repeated as necessary.
- the surface of the substrate particles can be coated with several layers of different metals.
- the outermost layer is a gold layer by adding the nickel-coated particles to an electroless gold plating solution and performing gold displacement plating.
- 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.
- 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 an LCD (Liquid Crystal Display), PDP. (Plasma Display Panel), OLED (Organic Light-Emitting Diodes) and other FPD (Flat Panel Display) boards and driver ICs that send image signals to them are widely used as materials for electrical connection. Yes.
- 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 diameter, coefficient of variation of particle diameter (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”.
- Phosphorus concentration 4 ml of aqua regia was added to 0.05 g of conductive fine particles, and the metal layer was dissolved and filtered by stirring under heating. Thereafter, the filtrate was analyzed for nickel and phosphorus contents using an ICP emission analyzer.
- the obtained paste-like composition was applied onto a release-treated PET film with a bar coater and dried to obtain an anisotropic conductive film.
- the obtained anisotropic conductive film was sandwiched between a full-scale aluminum vapor-deposited glass substrate having resistance measurement lines and a polyimide film substrate having a copper pattern formed at a pitch of 100 ⁇ m, and thermocompression bonded under a pressure bonding condition of 5 MPa and 200 ° C.
- a measurement sample was prepared. About this sample, the resistance value (initial resistance value) between electrodes was evaluated. Further, the resistance value between the electrodes after the measurement sample was allowed to stand for 1000 hours, 2000 hours, or 3000 hours at a temperature of 80 ° C. and a humidity of 100% was also measured in the same manner.
- Resistance value increase rate was calculated by the following formula, and the case where the resistance value increase rate was less than 1% was evaluated as “A”, and the case where the resistance value increase rate was 1% or more was evaluated as “B”.
- Resistance value increase rate (%) ((temperature 80 ° C., humidity 100%, resistance value after standing for a predetermined time) ⁇ (initial resistance value) / (initial resistance value)) ⁇ 100
- HITENOL ammonium polyoxyethylene styrenated phenyl ether sulfate
- Synthesis Example 2 Synthesis of vinyl polymer particle 2 In preparing an emulsion of polymerizable polysiloxane particles, “1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 355 parts of methanol were added to a four-necked flask.
- Synthesis Example 3 Synthesis of vinyl polymer particle 3 In preparing an emulsion of polymerizable polysiloxane particles, “1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 355 parts of methanol were added to a four-necked flask.
- Synthesis Example 4 Synthesis of vinyl polymer particle 4 In a four-necked flask equipped with a cooling tube, a thermometer, and a dropping port, 1000.0 parts of ion-exchanged water and 15.0 parts of 25% ammonia water were added and stirred. From the dropping port, 59.3 parts of vinyltrimethoxysilane, 40.7 parts of 3-methacryloxypropyltrimethoxysilane, and 170.0 parts of methanol are added as monomer components (seed forming monomers), and vinyltrimethoxy is added.
- Hydrolysis and condensation reactions of silane and 3-methacryloxypropyltrimethoxysilane were performed to prepare a dispersion of polymerizable polysiloxane particles (seed particles) having vinyl groups and methacryloyl groups.
- the number-based average particle diameter of the polysiloxane particles was 4.36 ⁇ m.
- 12.5 parts of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt (“HITENOL (registered trademark) NF-08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier is dissolved in 500 parts of ion-exchanged water.
- the emulsion after radical polymerization was subjected to solid-liquid separation, and the obtained cake was washed with ion-exchanged water and methanol, and then baked at 280 ° C. for 1 hour in a nitrogen atmosphere to obtain vinyl polymer particles 4.
- the number average particle size, particle size variation coefficient (CV value) and 10% K value of the vinyl polymer particles 4 were measured. The results are shown in Table 1.
- Synthesis Example 5 Synthesis of vinyl polymer particles 5 After appropriately changing the amounts of ion-exchanged water, methanol, and ammonia water to produce seed particles having a number-based average particle diameter of 4.50 ⁇ m, the types and use of absorbing monomers Instead of “divinylbenzene (“ DVB960 ”manufactured by Nippon Steel Chemical Co., Ltd .: a product containing 96% divinylbenzene, 4% ethylvinylbenzene, etc.) 500.0 parts”, “250 parts styrene and DVB960 (Nippon Steel Chemical) Vinyl polymer particles 5 were obtained in the same manner as in Synthesis Example 4 except that the product was changed to "250 parts” manufactured by the company, divinylbenzene content 96 mass%, ethylvinylbenzene 4% -containing product). The number average particle size, particle size variation coefficient (CV value) and 10% K value of the vinyl polymer particles 5 were measured. The results are shown in Table
- Synthesis Example 6 Synthesis of vinyl polymer particles 6 The amount of ion-exchanged water, methanol, and ammonia water was appropriately changed to produce seed particles having a number-based average particle size of 5.15 ⁇ m, and then the types and use of absorbing monomers.
- Vinyl polymer particles 6 were obtained in the same manner as in Synthesis Example 4 except that the content was changed to “25.0 parts of methacrylate” and dried for 4 hours at 80 ° C. in a nitrogen atmosphere instead of firing. The number average particle size, particle size variation coefficient (CV value) and 10% K value of the vinyl polymer particles 6 were measured. The results are shown in Table 1.
- Synthesis Example 7 Synthesis of vinyl polymer particles 7 The amount of ion-exchanged water, methanol, and ammonia water was appropriately changed to produce seed particles having a number-based average particle size of 3.25 ⁇ m, and then the types and use of absorbing monomers.
- Example 1 The above base particles (vinyl polymer particles 1) are etched with a sodium hydroxide aqueous solution, then contacted with a tin dichloride solution, and then immersed in a palladium dichloride solution (sensitizing- Activating method), palladium nuclei were formed. 10 parts of base material particles on which palladium nuclei were formed were added to 5000 parts of ion-exchanged water and sufficiently dispersed by ultrasonic irradiation to obtain a suspension. While this suspension was heated to 70 ° C. and stirred, 1000 mL of nickel plating solution heated to 70 ° C. was added.
- the nickel plating solution contains 38.0 g / L of glycine, 57.0 g / L of sodium acetate, 110.0 g / L of nickel sulfate, and 230 g / L of sodium hypophosphite (that is, nickel plating).
- the mass ratio of sodium acetate to glycine in the liquid was adjusted to 1.5), and the pH was adjusted to 6.3.
- the liquid temperature was maintained at 70 ° C., and after confirming that the generation of hydrogen gas was stopped, the mixture was stirred for 60 minutes. Then, solid-liquid separation was performed, and electroconductive fine particles 1 subjected to nickel plating were obtained by washing in the order of ion exchange water and methanol.
- the number average particle diameter, CV value, nickel layer thickness, and phosphorus concentration of the conductive fine particles 1 were measured. The results are shown in Table 2.
- Table 2 As a result of powder X-ray diffraction measurement of the conductive fine particles 1, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed.
- d (200) was 49.7 mm (4.97 nm)
- d (111) was 86.8 mm (8.68 nm)
- d (200) / d (111) 0.573.
- the results of the evaluation of the wet heat resistance of the conductive fine particles 1 were “A” when left for 1000 hours and “B” after left for 2000 hours. These evaluation results are shown in Table 3. *
- Example 2 In the same manner as in Example 1, 10 parts of base particles on which palladium nuclei were formed were added to 5000 parts of ion-exchanged water and sufficiently dispersed by ultrasonic irradiation to obtain a suspension. While this suspension was heated to 70 ° C. and stirred, 1000 mL of nickel plating solution heated to 70 ° C. was added. The nickel plating solution is 38.0 g / L glycine, 10.5 g / L malic acid, 76.0 g / L sodium acetate, 113.0 g / L nickel sulfate, and 230 g / L sodium hypophosphite.
- the mass ratio of sodium acetate to glycine in the nickel plating solution is 2.0
- the pH is adjusted to 6.8.
- the liquid temperature was maintained at 70 ° C., and after confirming that the generation of hydrogen gas was stopped, the mixture was stirred for 60 minutes. Thereafter, solid-liquid separation is performed, and ion-exchanged water and methanol are washed in this order. Then, the obtained conductive fine particles are heat-treated at 280 ° C. for 2 hours in a nitrogen (inert) atmosphere to perform nickel plating. Conductive fine particles 2 were obtained.
- the number average particle diameter, CV value, nickel layer thickness, and phosphorus concentration of the conductive fine particles 2 were measured. The results are shown in Table 2.
- Table 2 As a result of powder X-ray diffraction measurement of the conductive fine particles 2, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed.
- d (200) was 11 mm (1.1 nm)
- d (111) was 27.5 mm (2.75 nm)
- d (200) / d (111) 0.400.
- the results of the evaluation of the wet heat resistance of the conductive fine particles 2 were “A” when left for 1000 hours and “B” after left for 2000 hours. These evaluation results are shown in Table 3.
- Example 2 In the same manner as in Example 2 except that the heat treatment was performed at 260 ° C. for 2 hours in a nitrogen atmosphere instead of the heat treatment at 280 ° C. for 2 hours in the nitrogen atmosphere in Example 2, the conductive fine particles 4 were formed. Obtained. The number average particle diameter, CV value, nickel layer thickness, and phosphorus concentration of the conductive fine particles 4 were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 4, no diffraction lines attributed to the nickel lattice plane (200) were observed. Moreover, the result of the wet heat resistance evaluation after 1000 hours of the conductive fine particles 4 was “B”.
- Example 3 Instead of the nickel plating solution used in Example 1, lactic acid 52.2 g / L, malic acid 10.0 g / L, nickel sulfate 110.0 g / L, sodium hypophosphite 230 g / L, pH 4.
- Conductive fine particles 5 were obtained in the same manner as in Example 1 except that the nickel plating solution adjusted to 6 was used. The number average particle diameter, CV value, nickel layer thickness, and phosphorus concentration of the conductive fine particles 5 were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 5, no diffraction lines attributed to the nickel lattice plane (200) were observed. Moreover, the result of the wet heat resistance evaluation after 1000 hours of the conductive fine particles 5 was “B”.
- Example 3 Conductive fine particles 6 were obtained in the same manner as in Example 2 except that instead of the vinyl polymer particles 1, vinyl polymer particles 2 were used as base particles. The number average particle diameter of the obtained conductive fine particles 6, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 6, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- Example 4 Conductive fine particles 7 were obtained in the same manner as in Example 3 except that the conditions in the heat treatment were changed. The number average particle diameter of the obtained conductive fine particles 7, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 7, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- Example 5 Conductive fine particles 8 were obtained in the same manner as in Example 3 except that the conditions in the heat treatment were changed. The number average particle diameter, the thickness of the nickel layer, and the phosphorus concentration of the obtained conductive fine particles 8 were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 8, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- Example 6 Conductive fine particles 9 were obtained in the same manner as in Example 1 except that the vinyl polymer particles 3 were used as base particles instead of the vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 9, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 9, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- Example 7 Conductive fine particles 10 were obtained in the same manner as in Example 1 except that vinyl polymer particles 4 were used as base particles instead of vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 10, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 10, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- Example 8 Conductive fine particles 11 were obtained in the same manner as in Example 1 except that the vinyl polymer particles 5 were used as base particles instead of the vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 11, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 11, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- Example 9 Conductive fine particles 12 were obtained in the same manner as in Example 1 except that the vinyl polymer particles 6 were used as base particles instead of the vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 12, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 12, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- Example 10 Conductive fine particles 13 were obtained in the same manner as in Example 1 except that vinyl polymer particles 7 were used as base particles instead of vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 13, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 13, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
- the conductive fine particles 3 to 5 obtained in Comparative Examples 1 to 3 are inferior in heat-and-moisture resistance when measured in 1000 hours because diffraction lines attributed to the nickel lattice plane (200) are not observed.
- the conductive fine particles 1, 2 and 6 to 13 of Examples 1 to 10 have diffraction lines attributed to the nickel lattice plane (200), they have high heat and humidity resistance when measured in 1000 hours. Both are excellent.
- the conductive fine particles 6 to 8 having an average particle diameter of the base material of 3.0 ⁇ m in the conductive fine particles 6 to 8 having an average particle diameter of the base material of 3.0 ⁇ m, the larger d (200) / d (111), the longer the wet condition. It can be seen that the increase in resistance value can be effectively suppressed. It is considered that the moisture and heat resistance is more remarkably improved as the growth of the crystal of the nickel layer in the [200] direction progresses.
- the average particle diameter of the substrate is 2.3 ⁇ m (conductive fine particles) rather than 6 ⁇ m (conductive fine particles 1). It can be seen that 9) is superior in heat and moisture resistance even after a long time. Even if d (200) and d (111) of the nickel layer are equivalent, the increase in resistance value under wet heat conditions is more effectively suppressed by setting the average particle diameter of the substrate to 3.0 ⁇ m or less. be able to. The same effect is apparent from a comparison between the conductive fine particles 2 obtained in Example 2 and the conductive fine particles 6 obtained in Example 3.
- the conductive fine particles 2 and the conductive fine particles 6 also have the same d (200) and d (111) in the nickel layer, but the conductive fine particles 6 having a particle diameter of 3.0 ⁇ m or less have a resistance value under wet heat conditions. It turns out that a raise can be suppressed more effectively.
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Abstract
Description
1-1.導電性金属層
本発明の導電性微粒子は、基材粒子と、該基材粒子の表面を被覆する導電性金属層とを有している。そして、前記導電性金属層がニッケル層を含み、粉末X線回折測定したとき、ニッケル格子面(200)に帰属される回折線が観測され、すなわちニッケル格子面(200)に垂直な方向([200]方向)に結晶が成長している。これによって、導電性微粒子の耐湿熱性が向上できる。 1. Conductive fine particles 1-1. Conductive Metal Layer 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. When the conductive metal layer includes a nickel layer and powder X-ray diffraction measurement is performed, diffraction lines belonging to the nickel lattice plane (200) are observed, that is, a direction perpendicular to the nickel lattice plane (200) ([ 200] direction). Thereby, the wet heat resistance of the conductive fine particles can be improved.
なお、本発明でいうd(200)やd(111)等の結晶子径は、粉末X線回折測定により得られる回折線幅(半値幅)よりシェラーの式を用いて算出した値であり、具体的な結晶子径の測定方法については実施例において説明する。 In the powder X-ray diffraction measurement, in addition to the above (200) plane, for example, a diffraction line belonging to the (111) plane may be observed. In this case, d (200) / d (111) is preferably 0.05 or more, more preferably 0.2 or more, further preferably 0.20 or more (particularly more than 0.20), and further preferably 0. .35 or more. It can be said that the larger these values are, the clearer the existence of diffraction lines attributed to the (200) plane. In particular, when d (200) / d (111) satisfies the above range when the number average particle diameter of the conductive fine particles is 3 μm or less, the heat and moisture resistance can be maintained for a longer time. d (200) / d (111) is preferably less than 1, for example, more preferably 0.9 or less, and most preferably 0.8 or less. d (111) is usually less than 10 nm, preferably more than 2.0 nm.
In addition, crystallite diameters such as d (200) and d (111) referred to in the present invention are values calculated using the Scherrer equation from the diffraction line width (half width) obtained by powder X-ray diffraction measurement, A specific method for measuring the crystallite diameter will be described in Examples.
一方、他の導電性金属層を積層するときは、他の導電性金属層を構成する金属としては特に限定されないが、例えば、金、銀、銅、白金、鉄、鉛、アルミニウム、クロム、パラジウム、ロジウム、ルテニウム、アンチモン、ビスマス、ゲルマニウム、スズ、コバルト、インジウム及びニッケル-リン、ニッケル-ホウ素等の金属や金属化合物、及び、これらの合金等が挙げられる。これらの中でも、金、パラジウム、銀が導電性に優れており好ましい。導電性金属層は、例えば、ニッケル層-金層、ニッケル層-パラジウム層、ニッケル層-パラジウム層-金層、ニッケル層-銀層等の組合せが好ましく挙げられる。特に最外層として金層、又はパラジウム層を有することが好ましい。他の導電性金属層を積層するとき、他の導電性金属層が最表層となってもよい。
また、金やパラジウムなどの他の導電性金属層を構成する上記金属元素が、ニッケル元素と混在した金属層(合金状態の層を含む)を形成している形態も導電性金属層の好ましい形態の一つである。たとえば、ニッケル層を形成した後に、金の置換メッキを施した場合には、ニッケル層を構成するニッケル原子の少なくとも一部が金に置換されるために、上記のような導電性金属層となる。
前記ニッケル層は、基材粒子に直接形成してもよいし、下地として他の導電性金属層を基材粒子表面に形成し、その上にニッケル層を形成してもよいが、基材粒子に直接形成することが好ましい。 In addition to the nickel layer, the conductive metal layer may be laminated with another conductive metal layer or may not be laminated, but is preferably not laminated. When the other conductive metal layer is not laminated, the nickel layer becomes the outermost layer of the conductive metal layer.
On the other hand, when laminating another conductive metal layer, the metal constituting the other conductive metal layer is not particularly limited. 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. Among these, gold, palladium, and silver are preferable because of their excellent conductivity. Preferred examples of the conductive metal layer include 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. When laminating another conductive metal layer, the other conductive metal layer may be the outermost layer.
A preferred form of the conductive metal layer is a form in which the metal element constituting the other conductive metal layer such as gold or palladium forms a metal layer (including an alloyed layer) mixed with the nickel element. one of. For example, when gold plating is performed after the nickel layer is formed, at least a part of nickel atoms constituting the nickel layer is replaced with gold, so that the conductive metal layer is formed as described above. .
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.
前記基材粒子は、樹脂成分を含む樹脂粒子が好ましい。樹脂粒子を用いることで、弾性変形特性に優れた導電性微粒子が得られる。前記樹脂としては、例えば、メラミンホルムアルデヒド樹脂、メラミン-ベンゾグアナミン-ホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂等のアミノ樹脂;スチレン系樹脂、アクリル系樹脂、スチレン-アクリル樹脂等のビニル重合体;ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリイソブチレン、ポリブタジエン等のポリオレフィン;ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル類;ポリカーボネート類;ポリアミド類;ポリイミド類;フェノールホルムアルデヒド樹脂;オルガノポリシロキサン等が挙げられる。これらの樹脂は、単独で用いられてもよく、2種以上が併用されてもよい。電極の狭小化、或いは配線の微細化が進む電子部品実装において、今後、微細な導電性微粒子が要求されるため、基材粒子として、特に2.8μm未満の領域で、粒度分布が狭く、圧縮変形特性が制御された粒子が得られ易いという観点から、これらの中でも、ビニル重合体、アミノ樹脂、オルガノポリシロキサンが好ましく、ビニル重合体及びアミノ樹脂がより好ましく、特にビニル重合体が好ましい。ビニル重合体を含む材料は、ビニル基が重合して形成された有機系骨格を有し、加圧接続時の弾性変形に優れる。特に、ジビニルベンゼン及び/又はジ(メタ)アクリレートを重合成分として含むビニル重合体は、導電性金属被覆後の粒子強度の低下が少ない。 1-2. Base Particles The base particles are preferably resin particles containing a resin component. By using resin particles, conductive fine particles having excellent elastic deformation characteristics can be obtained. Examples of the resin 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, polychlorinated Polyolefins such as vinyl, polytetrafluoroethylene, polyisobutylene, and polybutadiene; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonates; polyamides; polyimides; phenol formaldehyde resin; These resins may be used alone or in combination of two or more. In electronic component mounting, where electrodes are becoming narrower or wiring is becoming finer, finer conductive particles will be required in the future. Therefore, the particle size distribution is narrow and compressed especially as a base particle in the region of less than 2.8 μm. Among these, vinyl polymers, amino resins, and organopolysiloxanes are preferable, vinyl polymers and amino resins are more preferable, and vinyl polymers are particularly preferable from the viewpoint that particles with controlled deformation characteristics are easily obtained. A material containing a vinyl polymer has an organic skeleton formed by polymerizing vinyl groups, and is excellent in elastic deformation during pressure connection. In particular, 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.
ビニル重合体粒子は、ビニル重合体により構成される。ビニル重合体は、ビニル系単量体(ビニル基含有単量体)を重合(ラジカル重合)することによって形成でき、このビニル系単量体はビニル系架橋性単量体とビニル系非架橋性単量体とに分けられる。なお、「ビニル基」には、炭素-炭素二重結合のみならず、(メタ)アクリロキシ基、アリル基、イソプロペニル基、ビニルフェニル基、イソプロペニルフェニル基のような官能基と重合性炭素-炭素二重結合から構成される置換基も含まれる。なお、本明細書において「(メタ)アクリロキシ基」、「(メタ)アクリレート」や「(メタ)アクリル」は、「アクリロキシ基及び/又はメタクリロキシ基」、「アクリレート及び/又はメタクリレート」や「アクリル及び/又はメタクリル」を示すものとする。 1-2-1. Vinyl polymer particles The 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. In this specification, “(meth) acryloxy group”, “(meth) acrylate” and “(meth) acryl” are “acryloxy group and / or methacryloxy group”, “acrylate and / or methacrylate” and “acryl and / Or methacryl ".
前記他の成分としては、特に限定されないが、ポリシロキサン成分が好ましい。ビニル重合体粒子に、ポリシロキサン骨格を導入することで、加圧接続時の弾性変形に優れるものとなる。 The vinyl polymer particles may contain other components to the extent that the properties of the vinyl polymer are not impaired. In this case, 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.
Although it does not specifically limit as said other component, A polysiloxane component is preferable. By introducing a polysiloxane skeleton into the vinyl polymer particles, it is excellent in elastic deformation at the time of pressure connection.
なお架橋性単量体の割合が少ないほど基材粒子の10%K値を小さくでき、例えば、4000N/mm2以下にすることもできる。目的とする10%K値によっては、架橋性単量体の割合は、好ましくは50質量%以下、より好ましくは40質量%以下、さらに好ましくは30質量%以下、特に好ましくは25質量%以下である。 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, for example, 20% by mass or more is preferable, more preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 70% by mass or more. The more the crosslinkable monomer, the harder the vinyl polymer particles. If the ratio of the crosslinkable monomer is within the above range, the restoring force is improved while maintaining excellent elastic deformation characteristics. Can be made. 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. Therefore, a high pressure may be required. Therefore, the ratio of the crosslinkable monomer is, for example, 98% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
In addition, 10% K value of a base particle can be made small, so that the ratio of a crosslinkable monomer is small, for example, can also be 4000 N / mm < 2 > or less. Depending on the target 10% K value, the proportion of the crosslinkable monomer is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less. is there.
ポリシロキサン粒子としては、前記第三の形態(ビニル重合体-ポリシロキサン間架橋)を形成し得るシラン系架橋性単量体を含む組成物を、(共)加水分解縮合して得られるポリシロキサン粒子が好ましく、特にビニル基含有ポリシロキサン粒子が好ましい。ポリシロキサン粒子がビニル基を有する場合、得られるビニル重合体粒子が、ビニル重合体とポリシロキサン骨格がポリシロキサンを構成するケイ素原子を介して結合するため、弾性変形性及び接触圧に特に優れたものとなる。ビニル基含有ポリシロキサン粒子は、例えば、ビニル基を有するジ又はトリアルコキシシランを含むシラン系単量体(混合物)を(共)加水分解縮合することによって製造できる。 In the production method (iii), it is preferable to use non-crosslinked or low-crosslinked polystyrene particles or polysiloxane particles as seed particles. By using polysiloxane particles as seed particles, a polysiloxane skeleton can be introduced into the vinyl polymer.
Polysiloxane particles obtained by (co) hydrolytic condensation of a composition containing a silane-based crosslinkable monomer capable of forming the third form (crosslinking between vinyl polymer and polysiloxane). Particles are preferred, and vinyl group-containing polysiloxane particles are particularly preferred. When the polysiloxane particles have a vinyl group, 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.
アミノ樹脂粒子を構成するアミノ樹脂は、アミノ化合物とホルムアルデヒドとの縮合物により構成されるものが好ましい。
前記アミノ化合物としては、例えば、ベンゾグアナミン、シクロヘキサンカルボグアナミン、シクロヘキセンカルボグアナミン、アセトグアナミン、ノルボルネンカルボグアナミン、スピログアナミン等のグアナミン化合物、メラミン等のトリアジン環構造を有する化合物等の多官能アミノ化合物が挙げられる。これらの中でも、多官能アミノ化合物が好ましく、トリアジン環構造を有する化合物がより好ましく、特にメラミン、グアナミン化合物(特にベンゾグアナミン)が好ましい。前記アミノ化合物は、1種のみを用いても良いし、2種以上を併用しても良い。 1-2-2. Amino resin particles The amino resin constituting the amino resin particles is preferably composed of a condensate of an amino compound and formaldehyde.
Examples of 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. . Among these, 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.
アミノ樹脂粒子の製造方法としては、例えば、特開2000-256432号公報、特開2002-293854号公報、特開2002-293855号公報、特開2002-293856号公報、特開2002-293857号公報、特開2003-55422号公報、特開2003-82049号公報、特開2003-138023号公報、特開2003-147039号公報、特開2003-171432号公報、特開2003-176330号公報、特開2005-97575号公報、特開2007-186716号公報、特開2008-101040号公報、特開2010-248475号公報等に記載のアミノ樹脂架橋粒子及びその製造方法を適用することが好ましい。 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.
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. JP-A-2003-55422, JP-A-2003-82049, JP-A-2003-138823, JP-A-2003-147039, JP-A-2003-171432, JP-A-2003-176330, It is preferable to apply the amino resin crosslinked particles described in JP-A-2005-97575, JP-A-2007-186716, JP-A-2008-101040, JP-A-2010-248475, and the production method thereof.
オルガノポリシロキサン粒子は、ビニル基を含有しないシラン系単量体(シラン系架橋性単量体、シラン系非架橋性単量体)の1種又は2種以上を(共)加水分解縮合することによって得られる。
前記ビニル基を含有しないシラン系単量体としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、フェニルトリメトキシシラン等の3官能性シラン系単量体;3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基を有するジ又はトリアルコキシシラン;3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン等のアミノ基を有するジ又はトリアルコキシシラン等が挙げられる。 1-2-3. Organopolysiloxane Particles Organopolysiloxane particles are composed of one or more silane monomers (silane crosslinkable monomers, silane noncrosslinkable monomers) that do not contain vinyl groups. It is obtained by decomposing and condensing.
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.
導電性微粒子が微細(具体的には、個数平均粒子径が10.0μm未満)になると、本発明の効果が一層顕著となる。よって、基材粒子の個数平均粒子径は、10.0μm未満が好ましく、より好ましくは3.0μm以下、さらに好ましくは2.8μm以下が好ましいが、より一層好ましくは、2.8μm未満、さらに一層好ましくは2.7μm以下、なお一層好ましくは2.6μm以下、特に好ましくは2.5μm以下であり、一方、1.0μm以上が好ましく、1.5μm以上がより好ましい。
この場合、基材粒子としては、上記ビニル重合体粒子、アミノ樹脂粒子、オルガノポリシロキサン粒子の中でも、架橋性単量体を含む単量体成分を重合することによって形成されたビニル重合体粒子、及び、トリアルコキシシランをシラン系架橋性単量体として用いたオルガノポリシロキサン粒子が好ましい。10%K値を制御し易い点で、架橋性単量体を含む単量体成分を重合することによって形成されたビニル重合体粒子がより好ましい。この微細なビニル重合体粒子を構成する全単量体に占める架橋性単量体(ビニル系架橋性単量体及びシラン系架橋性単量体の合計)の割合は、30質量%以上が好ましく、より好ましくは40質量%以上であり、さらに好ましくは50%質量以上である。
また、基材粒子(樹脂粒子)の個数平均粒子径が、1.0μm以上、50μm以下の範囲で比較的大粒子径であることも好ましい。例えば6μm以上、より好ましくは7μm以上、さらに好ましくは8μm以上の場合であることが好ましい。この場合、上限は、例えば25μm以下、より好ましくは23μm以下、さらに好ましくは20μm以下である。 The number average particle diameter of the substrate particles (resin particles) is preferably 1.0 μm or more, more preferably 1.1 μm or more, still more preferably 1.2 μm or more, still more preferably 1.3 μm or more, and 50 μm or less. Is preferable, more preferably 30 μm or less, and still more preferably 10 μm or less. The number-based variation coefficient (CV value) of the particle diameter of the substrate particles is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 5.0% or less, and still more preferably 4. 5% or less, particularly preferably 4.0% or less.
When the conductive fine particles are fine (specifically, the number average particle diameter is less than 10.0 μm), the effect of the present invention becomes more remarkable. Therefore, the number average particle diameter of the base particles is preferably less than 10.0 μm, more preferably 3.0 μm or less, still more preferably 2.8 μm or less, still more preferably less than 2.8 μm, even more. Preferably it is 2.7 μm or less, still more preferably 2.6 μm or less, particularly preferably 2.5 μm or less, while 1.0 μm or more is preferable, and 1.5 μm or more is more preferable.
In this case, as the base particles, among the vinyl polymer particles, amino resin particles, and organopolysiloxane particles, vinyl polymer particles formed by polymerizing a monomer component containing a crosslinkable monomer, Moreover, organopolysiloxane particles using trialkoxysilane as a silane-based crosslinkable monomer are preferred. Vinyl polymer particles formed by polymerizing a monomer component containing a crosslinkable monomer are more preferable in that the 10% K value can be easily controlled. The proportion of the crosslinkable monomer (total of vinyl-based crosslinkable monomer and silane-based crosslinkable monomer) in the total monomers constituting the fine vinyl polymer particles is preferably 30% by mass or more. More preferably, it is 40 mass% or more, More preferably, it is 50% mass or more.
It is also preferable that the number average particle diameter of the base particles (resin particles) is a relatively large particle diameter in the range of 1.0 μm or more and 50 μm or less. For example, it is preferably 6 μm or more, more preferably 7 μm or more, and still more preferably 8 μm or more. In this case, an upper limit is 25 micrometers or less, for example, More preferably, it is 23 micrometers or less, More preferably, it is 20 micrometers or less.
この場合、基材粒子としては、架橋性単量体を含む単量体成分を重合することによって形成されたビニル重合体粒子が好ましい。この軟質なビニル重合体粒子を構成する全単量体に占める架橋性単量体(ビニル系架橋性単量体及びシラン系架橋性単量体の合計)の割合は、50質量%以下が好ましく、より好ましくは40質量%以下であり、さらに好ましくは30質量%以下である。また、この軟質なビニル重合体粒子を構成する単量体成分に含まれる非架橋性単量体は、好ましい非架橋性単量体としてスチレン系単官能モノマー、アルキル(メタ)アクリレート類を含むものであることが好ましい。前記スチレン系単官能モノマーの中では、スチレンが好ましい。また、前記アルキル(メタ)アクリレート類の中では、メチル(メタ)アクリレート、アルキル基の炭素数が3以上であるアルキル(メタ)アクリレートが好ましく、10%K値を所定の範囲に調整することが容易である観点から、アルキル基の炭素数が3以上であるアルキル(メタ)アクリレートがより好ましく、ブチル(メタ)アクリレートが特に好ましい。非架橋性単量体の全量に占める、好ましい単量体(スチレン系単官能モノマー、アルキル(メタ)アクリレート類)の合計の割合は50質量%以上であることが好ましい。
基材粒子の10%K値の上限又は下限は、基材粒子の粒子径に応じて調整してもよい。粒子径に応じて調整することで、10%K値の制御効果をより確実に発揮させることができる。例えば、基材粒子の粒子径が3μm以下の場合、その10%K値は、3000N/mm2以上であることが好ましい。より好ましくは3500N/mm2以上、さらに好ましくは4000N/mm2超である。また、40000N/mm2以下であることが好ましく、より好ましくは30000N/mm2以下、さらに好ましくは25000N/mm2以下である。基材粒子の個数平均粒子径を3μm以下程度にまで小さくすると、従来の導電性微粒子(ニッケル層の結晶が[200]方向に成長していない導電性微粒子)では、湿熱性条件下で高圧縮時、接続抵抗値が上昇するという特有の不具合があった。小粒径、湿熱性条件、高圧縮が重なると、ニッケル層への負荷が大きくなり、導電性金属層が破断するためと思料される。本発明の導電性微粒子によれば、基材粒子の粒子径を3μm以下にしても、ニッケル層の結晶が[200]方向に成長しているためニッケル層が破断しにくい。よってこの粒子径3μm以下の場合に特有のこの課題を解決でき、10%K値の下限を比較的大きくすることが可能となる。 On the other hand, it is also a preferable aspect of the present invention that the base particles are softer. For example, it is also preferable 10% K value of the base particle is 100 N / mm 2 or more and 4000 N / mm 2 or less. When the 10% K value of the substrate particles is within the above range, the time during which the heat and humidity resistance can be exhibited becomes longer. That is, it can be seen that the use of soft base particles having a small 10% K value can suppress the increase in resistance value under a moist heat condition for a longer time. It is considered that during compression, the load is dispersed in the base particles and the load on the nickel layer is dispersed. In the case of expecting an effect of extending the heat and heat resistance duration, the 10% K value of the base particles is more preferably 300 N / mm 2 or more, further preferably 700 N / mm 2 or more, and particularly preferably 1000 N / mm 2 or more. is there. Further, it is more preferably 3900 N / mm 2 or less, further preferably 3850 N / mm 2 or less, particularly preferably 3800 N / mm 2 or less. This effect does not depend on the particle diameter of the base particles, but such soft base particles are particularly useful because the number average particle diameter of the base particles is, for example, 6 μm or more, more preferably 7 μm or more, More preferably, the thickness is 8 μm or more. An upper limit becomes like this. Preferably it is 25 micrometers or less, More preferably, it is 23 micrometers or less, More preferably, it is 20 micrometers or less. As the particle size increases, the amount of deformation during compression increases, but since the nickel layer crystals grow in the [200] direction, the nickel layer is less likely to break even under wet heat conditions. As a result, it is possible to more effectively suppress an increase in resistance value even under high compression under wet heat conditions.
In this case, the polymer particles are preferably vinyl polymer particles formed by polymerizing a monomer component containing a crosslinkable monomer. The proportion of the crosslinkable monomer (total of the vinyl-based crosslinkable monomer and the silane-based crosslinkable monomer) in the total monomers constituting the soft vinyl polymer particles is preferably 50% by mass or less. More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less. Further, the non-crosslinkable monomer contained in the monomer component constituting the soft vinyl polymer particles includes a styrene monofunctional monomer and alkyl (meth) acrylates as preferred non-crosslinkable monomers. It is preferable. Of the styrenic monofunctional monomers, styrene is preferred. Among the alkyl (meth) acrylates, methyl (meth) acrylate and alkyl (meth) acrylate having an alkyl group with 3 or more carbon atoms are preferable, and the 10% K value can be adjusted to a predetermined range. From an easy viewpoint, the alkyl (meth) acrylate whose carbon number of an alkyl group is 3 or more is more preferable, and a butyl (meth) acrylate is especially preferable. The total proportion of preferred monomers (styrene monofunctional monomers and alkyl (meth) acrylates) in the total amount of non-crosslinkable monomers is preferably 50% by mass or more.
The upper limit or lower limit of the 10% K value of the base particles may be adjusted according to the particle diameter of the base particles. By adjusting according to the particle diameter, the control effect of 10% K value can be more reliably exhibited. For example, when the particle diameter of the substrate particles is 3 μm or less, the 10% K value is preferably 3000 N / mm 2 or more. More preferably, it is 3500 N / mm 2 or more, more preferably more than 4000 N / mm 2 . Further, it is preferably 40000N / mm 2 or less, more preferably 30000 N / mm 2, more preferably not more than 25000N / mm 2. When the number average particle size of the base particles is reduced to about 3 μm or less, conventional conductive fine particles (conductive fine particles in which the nickel layer crystal does not grow in the [200] direction) are highly compressed under wet heat conditions. There was a peculiar defect that the connection resistance value increased. When small particle size, wet heat conditions, and high compression overlap, it is thought that the load on the nickel layer increases and the conductive metal layer breaks. According to the conductive fine particles of the present invention, even if the particle diameter of the base particles is 3 μm or less, the nickel layer is hardly broken because the crystal of the nickel layer grows in the [200] direction. Therefore, this problem peculiar when the particle diameter is 3 μm or less can be solved, and the lower limit of the 10% K value can be made relatively large.
前記導電性微粒子の個数平均粒子径は、1.0μm以上が好ましく、より好ましくは1.1μm以上、さらに好ましくは1.2μm以上、一層好ましくは1.3μm以上、特に好ましくは1.4μm以上であり、好ましくは50μm以下が好ましく、より好ましくは30μm以下、さらに好ましくは10μm以下である。また前記導電性微粒子の粒子径の個数基準の変動係数(CV値)は、10.0%以下が好ましく、より好ましくは8.0%以下、さらに好ましくは5.0%以下、一層好ましくは4.5%以下、特に好ましくは4.0%以下である。
導電性微粒子が微細(具体的には、個数平均粒子径が10.0μm未満)になると、基材粒子を10.0μm未満にした場合と同様、湿熱性条件下でも導電性微粒子の接続抵抗値上昇を効果的に抑制できる。よって、本発明の効果が一層顕著となる理由から、個数平均粒子径は、10.0μm未満が好ましく、より好ましくは3.2μm以下、さらに好ましくは3.0μm以下が好ましいが、より一層好ましくは、2.8μm以下、さらに一層好ましくは2.7μm以下、なお一層好ましくは2.6μm以下であり、一方、1.1μm以上が好ましく、1.6μm以上がより好ましい。
一方、基材粒子が軟質であると、上述の通りニッケル層の結晶が[200]方向に成長しているため、湿熱性条件下でも導電性微粒子の接続抵抗値上昇をより効果的に抑制できる。軟質な基材粒子が特に有用となるのは、導電性微粒子の個数平均粒子径が、例えば、6.3μm以上、より好ましくは7.3μm以上、さらに好ましくは8.3μm以上の場合である。上限は、例えば25μm以下、より好ましくは23μm以下、さらに好ましくは20μm以下である。 1-3. Conductive fine particles The number average particle diameter of the conductive fine particles is preferably 1.0 μm or more, more preferably 1.1 μm or more, still more preferably 1.2 μm or more, still more preferably 1.3 μm or more, and particularly preferably 1. It is 4 μm or more, preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 10 μm or less. The number-based variation coefficient (CV value) of the conductive fine particles is preferably 10.0% or less, more preferably 8.0% or less, still more preferably 5.0% or less, and still more preferably 4%. .5% or less, particularly preferably 4.0% or less.
When the conductive fine particles are fine (specifically, the number average particle diameter is less than 10.0 μm), the connection resistance value of the conductive fine particles even under wet and heat conditions is the same as when the base particles are less than 10.0 μm. The rise can be effectively suppressed. Therefore, the number average particle diameter is preferably less than 10.0 μm, more preferably 3.2 μm or less, still more preferably 3.0 μm or less, even more preferably, for the reason that the effects of the present invention become more remarkable. 2.8 μm or less, even more preferably 2.7 μm or less, even more preferably 2.6 μm or less, while 1.1 μm or more is preferable and 1.6 μm or more is more preferable.
On the other hand, if the base particles are soft, the crystal of the nickel layer grows in the [200] direction as described above, so that the increase in the connection resistance value of the conductive fine particles can be more effectively suppressed even under wet and heat conditions. . The soft base particles are particularly useful when the number average particle diameter of the conductive fine particles is, for example, 6.3 μm or more, more preferably 7.3 μm or more, and further preferably 8.3 μm or more. An upper limit is 25 micrometers or less, for example, More preferably, it is 23 micrometers or less, More preferably, it is 20 micrometers or less.
前記導電性微粒子は、無電解めっき法により製造でき、この微粒子中のニッケル層において(200)面に垂直な方向に結晶を成長させるには、無電解めっき工程で特有の処理が必要となる。すなわち無電解めっき工程におけるめっき液(ニッケル塩含有めっき液)がグリシンと酢酸ナトリウムを含むこと、言い換えればニッケルめっき時にグリシンと酢酸ナトリウムが共存することが重要である。さらに、(i)グリシンに対する酢酸ナトリウムの質量割合(酢酸ナトリウム/グリシン)を1.8以下(好ましくは1.7以下、さらに好ましくは1.6以下)にすること、又は(ii)グリシンに対する酢酸ナトリウムの質量割合が1.8を超える場合(好ましくは1.9以上、さらに好ましくは2.0以上の場合)には、めっき後に、窒素などの不活性雰囲気下、270℃以上(好ましくは275℃以上、さらに好ましくは280℃以上)で熱処理することによって、本発明の導電性微粒子を得ることができる。
前記(i)の場合、グリシンに対する酢酸ナトリウムの質量割合の下限は、例えば0.5以上、好ましくは0.8以上、さらに好ましくは1.0以上である。
前記(ii)の場合、グリシンに対する酢酸ナトリウムの質量割合の上限は3以下であることが好ましく、より好ましくは2.5以下である。不活性雰囲気下での熱処理温度は、350℃以下が好ましく、より好ましくは320℃以下、さらに好ましくは300℃以下である。不活性雰囲気下での熱処理時間の下限は、好ましくは0.1時間以上、より好ましくは1時間以上であり、前記熱処理時間の上限は、好ましくは20時間以下、より好ましくは10時間以下、さらに好ましくは5時間以下である。 1-4. Method for Producing Conductive Fine Particles The conductive fine particles can be produced by an electroless plating method. In order to grow crystals in a direction perpendicular to the (200) plane in the nickel layer in the fine particles, a special treatment in the electroless plating step is performed. Is required. That is, it is important that the plating solution (nickel salt-containing plating solution) in the electroless plating step contains glycine and sodium acetate, in other words, glycine and sodium acetate coexist during nickel plating. Furthermore, (i) the mass ratio of sodium acetate to glycine (sodium acetate / glycine) is 1.8 or less (preferably 1.7 or less, more preferably 1.6 or less), or (ii) acetic acid to glycine When the mass ratio of sodium exceeds 1.8 (preferably 1.9 or more, more preferably 2.0 or more), after plating, 270 ° C. or more (preferably 275) under an inert atmosphere such as nitrogen. The conductive fine particles of the present invention can be obtained by heat treatment at a temperature of not lower than ° C., more preferably not lower than 280 ° C.
In the case of (i), the lower limit of the mass ratio of sodium acetate to glycine is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 1.0 or more.
In the case of (ii), the upper limit of the mass ratio of sodium acetate to glycine is preferably 3 or less, more preferably 2.5 or less. The heat treatment temperature in an inert atmosphere is preferably 350 ° C. or lower, more preferably 320 ° C. or lower, and further preferably 300 ° C. or lower. The lower limit of the heat treatment time under an inert atmosphere is preferably 0.1 hour or more, more preferably 1 hour or more, and the upper limit of the heat treatment time is preferably 20 hours or less, more preferably 10 hours or less, Preferably it is 5 hours or less.
エッチング処理工程では、クロム酸、無水クロム酸-硫酸混合液、過マンガン酸等の酸化剤;塩酸、硫酸、フッ酸、硝酸等の強酸;水酸化ナトリウム、水酸化カリウム等の強アルカリ溶液;その他市販の種々のエッチング剤等を用いて、基材粒子の表面に親水性付与し、その後の無電解めっき液に対する濡れ性を高める。また、微小な凹凸を形成させ、その凹凸のアンカー効果によって、無電解めっき後の基材粒子と導電性金属層との密着性の向上を図る。 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., imparting hydrophilicity to the surface of the substrate particles, and increasing the wettability to the subsequent electroless plating solution. In addition, minute unevenness is formed, and the adhesion between the substrate particles after electroless plating and the conductive metal layer is improved by the anchor effect of the unevenness.
前記触媒化処理では、基材粒子表面に貴金属イオンを捕捉させた後、これを還元して前記貴金属を基材粒子表面に担持させ、基材粒子の表面に次工程の無電解めっきの起点となりうる触媒層を形成させる。基材粒子自体が貴金属イオンの捕捉能を有さない場合、触媒化を行う前に、表面改質処理を行うことも好ましい。表面改質処理は、表面処理剤を溶解した水又は有機溶媒に、基材粒子を接触させることで行うことができる。 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. In the case where 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.
無電解めっき工程では、上述の特有の処理(グリシンと酢酸ナトリウムの併用と、これらの割合に応じた熱処理の有無)を施す以外は、通常の無電解めっき工程が採用される。すなわち無電解めっき工程では、まず、触媒化基材粒子を水に十分に分散させ、触媒化基材粒子の水性スラリーを調製する。ここで、安定した導電特性を発現させるためには、触媒化基材粒子をめっき処理を行う水性媒体に十分に分散させておくことが好ましい。触媒化基材粒子が凝集した状態で無電解めっき処理を行うと、基材粒子同士の接触面に未処理面(導電性金属層が存在しない面)が生じるからである。触媒化基材粒子を水性媒体に分散させる手段としては、例えば、通常攪拌装置、高速攪拌装置、コロイドミル又はホモジナイザーのような剪断分散装置など従来公知の分散手段や、超音波や分散剤(界面活性剤等)を用いれば良い。 Electroless Plating Step In the electroless plating step, a normal electroless plating step is employed except that the above-described specific treatment (combination of glycine and sodium acetate and the presence or absence of heat treatment according to these ratios) is performed. That is, in the electroless plating step, first, the catalyst base material particles are sufficiently dispersed in water to prepare an aqueous slurry of the catalyst base material particles. Here, in order to develop stable conductive properties, it is preferable to sufficiently disperse the catalyzed base particles in an aqueous medium for plating. This is because when the electroless plating treatment is performed in a state where the catalyst base material particles are aggregated, an untreated surface (a surface on which no conductive metal layer is present) is formed on the contact surface between the base material particles. Examples of means for dispersing the catalyzed substrate particles in the aqueous medium include 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, and ultrasonic waves and a dispersing agent (interface). An activator or the like may be used.
前記無電解めっき液のpHは、限定されないが、好ましくは6~14である。また、無電解めっき液の液温も特に限定されないが、例えば30~100℃である。 As a complexing agent, the above glycine acts as it. Therefore, in the present invention, the use of other complexing agents is not essential, but other complexing agents may be used as necessary. Other complexing agents include citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, gluconic acid or carboxylic acids (salts) such as alkali metal salts and ammonium salts thereof; amino acids such as glutamic acid; ethylenediamine, alkylamine, etc. Aminic acid; other ammonium, EDTA, pyrophosphoric acid (salt); and the like. The concentration of glycine is, for example, about 20 to 50 g per 1 L of plating solution, and the concentration of complexing agent is, for example, about 20 to 150 g per 1 L of plating solution.
The pH of the electroless plating solution is not limited, but is preferably 6 to 14. Further, the temperature of the electroless plating solution is not particularly limited, but is, for example, 30 to 100 ° C.
導電性微粒子はその表面が平滑であっても凹凸状であっても良いが、バインダー樹脂を効果的に排除して電極との接続を行える点で複数の突起を有することが好ましい。突起を有することで、導電性微粒子を電極間の接続に用いた際の接続信頼性を高めることができる。 2. Conductive fine particles having protrusions 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.
本発明の導電性微粒子は、表面の少なくとも一部に絶縁層を有する態様(絶縁被覆導電性微粒子)であってもよい。このように表面の導電性金属層にさらに絶縁層が積層されていると、高密度回路の形成時や端子接続時等に生じやすい横導通を防ぐことができる。 3. Insulating Coated Conductive Fine Particle 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.
絶縁粒子はその表面に導電性微粒子への付着性を高めるため官能基を有していても良い。前記官能基としては、アミノ基、エポキシ基、カルボキシル基、リン酸基、シラノール基、アンモニウム基、スルホン酸基、チオール基、ニトロ基、ニトリル基、オキサゾリン基、ピロリドン基、スルホニル基、水酸基等が挙げられる。 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. When the average particle diameter of the insulating particles is within the above range, 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.
本発明の導電性微粒子は、異方性導電材料として有用である。
前記異方性導電材料としては、前記導電性微粒子がバインダー樹脂に分散してなるものが挙げられる。異方性導電材料の形態は特に限定されず、例えば、異方性導電フィルム、異方性導電ペースト、異方性導電接着剤、異方性導電インク等様々な形態が挙げられる。これらの異方性導電材料を相対向する基材同士や電極端子間に設けることにより、良好な電気的接続が可能になる。なお、本発明の導電性微粒子を用いた異方性導電材料には、液晶表示素子用導通材料(導通スペーサー及びその組成物)も含まれる。 4). Anisotropic Conductive Material The conductive fine particles of the present invention are useful as an anisotropic conductive material.
Examples of 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).
これらの用途の中でも、本発明の異方性導電性材料はFPDのFOG接続、COG接続、ならびにタッチパネル引き出し回路とFPC接続用に好適に用いられる。異方性導電材料の形態としてはペースト状であってもフィルム状であっても良いが、接続信頼性をより高められる点でフィルム状(異方性導電フィルム)であることが好ましい。 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 an LCD (Liquid Crystal Display), PDP. (Plasma Display Panel), OLED (Organic Light-Emitting Diodes) and other FPD (Flat Panel Display) boards and driver ICs that send image signals to them are widely used as materials for electrical connection. Yes. Specifically, a connection between a signal output electrode such as a TCP (Tape Carrier Package) or COF (Chip on Film) package, which is equipped with a driver IC that transmits a signal for driving the panel, and the LCD panel (generally FOG and COG (Chip) which mounts the driver IC on the LCD panel as a pair chip and connection with a printed circuit board (PWB: Printed Wiring Board) that inputs signals to these, such as TCP, COF, etc. In addition to being used for on-glass connection, it is also used for connection between a touch panel lead-out circuit and an FPC (flexible printed wiring board) or camera module.
Among these uses, 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.
1-1.個数平均粒子径、粒子径の変動係数(CV値)
粒度分布測定装置(ベックマンコールター社製、「コールターマルチサイザーIII型」)により30000個の粒子の粒子径を測定し、個数基準の平均粒子径、粒子径の標準偏差を求めるとともに、下記式に従って粒子径の個数基準のCV値(変動係数)を算出した。
粒子の変動係数(%)=100×(粒子径の標準偏差/個数基準平均粒子径)
なお、基材粒子では、基材粒子0.005部に界面活性剤(第一工業製薬社製、「ハイテノール(登録商標) N-08」)の1%水溶液20部を加え、超音波で10分間分散させた分散液を測定試料とした。シード粒子では、加水分解、縮合反応で得られた分散液を、界面活性剤(第一工業製薬社製、「ハイテノール(登録商標) N-08」)の1%水溶液により希釈したものを測定試料とした。 1. Evaluation method 1-1. Number average particle diameter, coefficient of variation of particle diameter (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)
In addition, in the base particle, 20 parts of a 1% aqueous solution of a surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “Hytenol (registered trademark) N-08”) is added to 0.005 part of the base particle, and ultrasonically applied. A dispersion liquid dispersed for 10 minutes was used as a measurement sample. For seed particles, 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.
粉末X線回折装置(リガク社製、「RINT(登録商標)-TTRIII」)を使用して、導電性微粒子についてX線回折測定を行った。次いで、解析ソフトとして総合粉末X線解析ソフトウエア(リガク社製、「PDKL」)を用い、ミラー指数(200)の格子面に帰属されるピーク(回折線)の幅(積分幅)から、Scherrerの式に基づいて、該格子面に垂直方向の結晶子径d(200)を計算した。また、同様にして、各実施例についてミラー指数(111)の格子面に垂直方向の結晶子径d(111)も計算した。 1-2. Diffraction Line and Crystallite Diameter X-ray diffraction measurement was performed on the conductive fine particles using a powder X-ray diffractometer (manufactured by Rigaku Corporation, “RINT (registered trademark) -TTRIII”). Next, using comprehensive powder X-ray analysis software (“PDKL”, manufactured by Rigaku Corporation) as analysis software, Scherrer is obtained from the width (integration width) of the peak (diffraction line) attributed to the lattice plane of the Miller index (200). Based on the above formula, the crystallite diameter d (200) in the direction perpendicular to the lattice plane was calculated. Similarly, the crystallite diameter d (111) in the direction perpendicular to the lattice plane of the Miller index (111) was also calculated for each example.
フロー式粒子像解析装置(シスメックス社製、「FPIA(登録商標)-3000」)を用いて、基材粒子3000個の粒子径、導電性微粒子3000個の粒子径を測定し、基材粒子の個数平均粒子径X(μm)、導電性微粒子の個数平均粒子径Y(μm)、CV値(%)を求めた。そして、下記式に従って導電性金属層の膜厚を算出した。
導電性金属層膜厚(μm)=(Y-X)/2 1-3. Conductive metal layer thickness Using a flow-type particle image analyzer ("FPIA (registered trademark) -3000" manufactured by Sysmex Corporation), the particle diameter of 3000 base particles and 3000 conductive particles are measured. Then, the number average particle diameter X (μm) of the base particles, the number average particle diameter Y (μm) of the conductive fine particles, and the CV value (%) were determined. And the film thickness of the electroconductive metal layer was computed according to the following formula.
Conductive metal layer thickness (μm) = (Y−X) / 2
導電性微粒子0.05gに王水4mlを加え、加熱下で攪拌することにより金属層を溶解し、ろ別した。その後、ろ液をICP発光分析装置を用いて、ニッケル及びリンの含有量を分析した。 1-4. Phosphorus concentration 4 ml of aqua regia was added to 0.05 g of conductive fine particles, and the metal layer was dissolved and filtered by stirring under heating. Thereafter, the filtrate was analyzed for nickel and phosphorus contents using an ICP emission analyzer.
導電性微粒子10質量部(以下、質量部については単に「部」と表す)に、バインダー樹脂としてのエポキシ樹脂(三菱化学社製、「JER828」)を100部、硬化剤(三新化学社製、「サンエイド(登録商標) SI-150」)2部、及びトルエン100部を加えた。この混合物に、1mmのジルコニアビーズ50部を加えて、ステンレス製の2枚攪拌羽根を用いて300rpmで10分間分散を行い、ペースト状組成物を得た。得られたペースト状組成物をバーコーターで剥離処理PETフィルム上に塗布し、乾燥させて、異方性導電フィルムを得た。
得られた異方性導電フィルムを、抵抗測定用の線を有する全面アルミ蒸着ガラス基板と、100μmピッチで銅パターンを形成したポリイミドフィルム基板間に挟み込み、5MPa、200℃の圧着条件で熱圧着して測定試料を作製した。この試料について、電極間の抵抗値(初期抵抗値)を評価した。また、測定試料を、温度80℃、湿度100%で1000時間、2000時間、又は3000時間放置した後の電極間の抵抗値についてもそれぞれ同様に測定した。
下記式により抵抗値上昇率を求め、抵抗値上昇率が1%未満の場合を「A」、抵抗値上昇率が1%以上の場合を「B」と評価した。
抵抗値上昇率(%)=((温度80℃、湿度100%、所定時間放置後の抵抗値)-(初期抵抗値)/(初期抵抗値))×100 1-5. Wet and heat resistance evaluation 100 parts of epoxy resin (manufactured by Mitsubishi Chemical Corporation, “JER828”) as a binder resin and 10 parts by weight of conductive fine particles (hereinafter, “parts” are simply referred to as “parts”), a curing agent (Sanshin 2 parts of “Sun Aid (registered trademark) SI-150” manufactured by Kagaku Co., Ltd.) and 100 parts of toluene were added. To this mixture, 50 parts of 1 mm zirconia beads were added and dispersed at 300 rpm for 10 minutes using two stainless steel stirring blades to obtain a paste-like composition. The obtained paste-like composition was applied onto a release-treated PET film with a bar coater and dried to obtain an anisotropic conductive film.
The obtained anisotropic conductive film was sandwiched between a full-scale aluminum vapor-deposited glass substrate having resistance measurement lines and a polyimide film substrate having a copper pattern formed at a pitch of 100 μm, and thermocompression bonded under a pressure bonding condition of 5 MPa and 200 ° C. A measurement sample was prepared. About this sample, the resistance value (initial resistance value) between electrodes was evaluated. Further, the resistance value between the electrodes after the measurement sample was allowed to stand for 1000 hours, 2000 hours, or 3000 hours at a temperature of 80 ° C. and a humidity of 100% was also measured in the same manner.
The resistance value increase rate was calculated by the following formula, and the case where the resistance value increase rate was less than 1% was evaluated as “A”, and the case where the resistance value increase rate was 1% or more was evaluated as “B”.
Resistance value increase rate (%) = ((temperature 80 ° C., humidity 100%, resistance value after standing for a predetermined time) − (initial resistance value) / (initial resistance value)) × 100
微小圧縮試験機(島津製作所製「MCT-W500」)を用いて、室温(25℃)において、試料台上に散布した試料粒子1個について、直径50μmの円形平板圧子を用いて、「標準表面検出」モードで粒子の中心方向へ一定の負荷速度(2.2295mN/秒)で荷重をかけた。そして、圧縮変位が粒子径の10%となったときの荷重(mN)を測定し、得られた圧縮荷重、粒子の圧縮変位及び粒子径から、10%K値を算出した。なお、測定は各試料について、異なる10個の粒子に対して行い、平均した値を測定値とした。 1-6. 10% K value of substrate particles A circular flat plate with a diameter of 50 μm per sample particle dispersed on a sample stage at room temperature (25 ° C.) using a micro compression tester (“MCT-W500” manufactured by Shimadzu Corporation) Using an indenter, a load was applied at a constant load speed (2.2295 mN / sec) toward the center of the particle in the “standard surface detection” mode. Then, the load (mN) when the compression displacement became 10% of the particle diameter was measured, and a 10% K value was calculated from the obtained compression load, particle compression displacement, and particle diameter. In addition, the measurement was performed on 10 different particles for each sample, and the average value was used as the measurement value.
2-1.合成例1:ビニル重合体粒子1の合成
冷却管、温度計、滴下口を備えた四つ口フラスコに、イオン交換水1800部と、25%アンモニア水24部、メタノール355部を入れ、攪拌下、滴下口から3-メタクリロキシプロピルトリメトキシシラン100部及びメタノール245部の混合液を添加して、3-メタクリロキシプロピルトリメトキシシランの加水分解、縮合反応を行って、メタクリロイル基を有するポリシロキサン粒子(重合性ポリシロキサン粒子)の乳濁液を調製した。このポリシロキサン粒子の個数平均粒子径は3.02μmであった。 2. 2. Preparation of substrate particles 2-1. Synthesis Example 1: Synthesis of vinyl polymer particle 1 In a four-necked flask equipped with a cooling tube, a thermometer, and a dripping port, 1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 355 parts of methanol were added and stirred. A polysiloxane having a methacryloyl group is obtained by adding a liquid mixture of 100 parts of 3-methacryloxypropyltrimethoxysilane and 245 parts of methanol from the dropping port to hydrolyze and condense 3-methacryloxypropyltrimethoxysilane. An emulsion of particles (polymerizable polysiloxane particles) was prepared. The number average particle size of the polysiloxane particles was 3.02 μm.
重合性ポリシロキサン粒子の乳濁液を調製するにあたり、「四つ口フラスコに、イオン交換水1800部と、25%アンモニア水24部、メタノール355部を入れ、攪拌下、滴下口から3-メタクリロキシプロピルトリメトキシシラン100部及びメタノール245部の混合液を添加」することに代えて、「四つ口フラスコに、イオン交換水1800部と、25%アンモニア水24部、メタノール450部を入れ、攪拌下、滴下口から3-メタクリロキシプロピルトリメトキシシラン150部及びメタノール500部の混合液を添加」したこと以外は、合成例1と同様にしてビニル重合体粒子2を作製した。このとき中間生成物であるポリシロキサン粒子の個数平均粒子径は1.50μmであった。また、得られたビニル重合体粒子2の個数平均粒子径、粒子径の変動係数(CV値)および10%K値を測定した。結果を表1に示す。 2-2. Synthesis Example 2: Synthesis of vinyl polymer particle 2 In preparing an emulsion of polymerizable polysiloxane particles, “1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 355 parts of methanol were added to a four-necked flask. In place of adding a mixed solution of 100 parts of 3-methacryloxypropyltrimethoxysilane and 245 parts of methanol from the dropping port with stirring, 1800 parts of ion-exchanged water and 25% Vinyl was added in the same manner as in Synthesis Example 1 except that 24 parts of ammonia water and 450 parts of methanol were added and a mixed solution of 150 parts of 3-methacryloxypropyltrimethoxysilane and 500 parts of methanol was added from the dropping port under stirring. Polymer particle 2 was produced. At this time, the number average particle diameter of the polysiloxane particles as an intermediate product was 1.50 μm. Further, the number average particle diameter, the coefficient of variation (CV value) of the particle diameter, and the 10% K value of the obtained vinyl polymer particles 2 were measured. The results are shown in Table 1.
重合性ポリシロキサン粒子の乳濁液を調製するにあたり、「四つ口フラスコに、イオン交換水1800部と、25%アンモニア水24部、メタノール355部を入れ、攪拌下、滴下口から3-メタクリロキシプロピルトリメトキシシラン100部及びメタノール245部の混合液を添加」することに代えて、「四つ口フラスコに、イオン交換水1800部と、25%アンモニア水24部、メタノール550部を入れ、攪拌下、滴下口から3-メタクリロキシプロピルトリメトキシシラン100部及びメタノール50部の混合液を添加」したこと以外は、合成例1と同様にしてビニル重合体粒子3を作製した。このとき中間生成物であるポリシロキサン粒子の個数平均粒子径は1.15μmであった。また、得られたビニル重合体粒子3の個数平均粒子径、粒子径の変動係数(CV値)および10%K値を測定した。結果を表1に示す。 2-3. Synthesis Example 3: Synthesis of vinyl polymer particle 3 In preparing an emulsion of polymerizable polysiloxane particles, “1800 parts of ion-exchanged water, 24 parts of 25% ammonia water, and 355 parts of methanol were added to a four-necked flask. In place of adding a mixed solution of 100 parts of 3-methacryloxypropyltrimethoxysilane and 245 parts of methanol from the dropping port with stirring, 1800 parts of ion-exchanged water and 25% Vinyl was added in the same manner as in Synthesis Example 1 except that 24 parts of ammonia water and 550 parts of methanol were added and a mixed solution of 100 parts of 3-methacryloxypropyltrimethoxysilane and 50 parts of methanol was added from the dropping port under stirring. Polymer particles 3 were produced. At this time, the number average particle diameter of the polysiloxane particles as an intermediate product was 1.15 μm. Further, the number average particle diameter, the coefficient of variation (CV value) of the particle diameter, and the 10% K value of the obtained vinyl polymer particles 3 were measured. The results are shown in Table 1.
冷却管、温度計、滴下口を備えた四つ口フラスコに、イオン交換水1000.0部と、25%アンモニア水15.0部を入れ、攪拌下、滴下口から、単量体成分(シード形成モノマー)としてビニルトリメトキシシラン59.3部、3-メタクリロキシプロピルトリメトキシシラン40.7部、及びメタノール170.0部を添加し、ビニルトリメトキシシラン及び3-メタクリロキシプロピルトリメトキシシランの加水分解、縮合反応を行って、ビニル基及びメタクリロイル基を有する重合性ポリシロキサン粒子(シード粒子)の分散液を調製した。このポリシロキサン粒子の個数基準の平均粒子径は4.36μmであった。
次いで、乳化剤としてポリオキシエチレンスチレン化フェニルエーテル硫酸エステルアンモニウム塩(第一工業製薬社製「ハイテノール(登録商標)NF-08」)の20%水溶液12.5部をイオン交換水500部に溶解した溶液に、単量体成分(吸収モノマー)としてジビニルベンゼン(新日鐡化学社製「DVB960」:ジビニルベンゼン96%、エチルビニルベンゼン等4%含有品)500.0部と、2,2’-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬工業社製「V-65」)12.0部とを溶解した溶液を加え、乳化分散させて単量体成分(吸収モノマー)の乳化液を調製した。乳化分散の開始から2時間後、得られた乳化液を、ポリシロキサン粒子(シード粒子)の分散液中に添加して、さらに攪拌を行った。乳化液の添加から1時間後、混合液をサンプリングして顕微鏡で観察を行ったところ、ポリシロキサン粒子が吸収モノマーを吸収して肥大化していることが確認された。
次いで、ポリオキシエチレンスチレン化フェニルエーテル硫酸エステルアンモニウム塩(第一工業製薬社製「ハイテノール(登録商標)NF-08」)の20%水溶液25.0部を加え、窒素雰囲気下で反応液を65℃まで昇温させて、65℃で2時間保持し、単量体成分のラジカル重合を行った。ラジカル重合後の乳濁液を固液分離し、得られたケーキをイオン交換水、メタノールで洗浄した後、窒素雰囲気下280℃で1時間焼成し、ビニル重合体粒子4を得た。ビニル重合体粒子4の個数平均粒子径、粒子径の変動係数(CV値)および10%K値を測定した。結果を表1に示す。 2-4. Synthesis Example 4: Synthesis of vinyl polymer particle 4 In a four-necked flask equipped with a cooling tube, a thermometer, and a dropping port, 1000.0 parts of ion-exchanged water and 15.0 parts of 25% ammonia water were added and stirred. From the dropping port, 59.3 parts of vinyltrimethoxysilane, 40.7 parts of 3-methacryloxypropyltrimethoxysilane, and 170.0 parts of methanol are added as monomer components (seed forming monomers), and vinyltrimethoxy is added. Hydrolysis and condensation reactions of silane and 3-methacryloxypropyltrimethoxysilane were performed to prepare a dispersion of polymerizable polysiloxane particles (seed particles) having vinyl groups and methacryloyl groups. The number-based average particle diameter of the polysiloxane particles was 4.36 μm.
Next, 12.5 parts of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt (“HITENOL (registered trademark) NF-08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier is dissolved in 500 parts of ion-exchanged water. In this solution, 500.0 parts of divinylbenzene (“DVB960” manufactured by Nippon Steel Chemical Co., Ltd .: a product containing 96% divinylbenzene, 4% ethylvinylbenzene, etc.) as a monomer component (absorbing monomer) and 2,2 ′ -Emulsification of monomer component (absorbing monomer) by adding a solution of 12.0 parts of azobis (2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.) A liquid was prepared. Two hours after the start of emulsification dispersion, the obtained emulsion was added to a dispersion of polysiloxane particles (seed particles), and further stirred. One hour after the addition of the emulsified liquid, the mixed liquid was sampled and observed with a microscope. As a result, it was confirmed that the polysiloxane particles were absorbed and absorbed.
Next, 25.0 parts of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt (“Hitenol (registered trademark) NF-08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added, and the reaction solution was added under nitrogen atmosphere. The temperature was raised to 65 ° C. and held at 65 ° C. for 2 hours to perform radical polymerization of the monomer component. The emulsion after radical polymerization was subjected to solid-liquid separation, and the obtained cake was washed with ion-exchanged water and methanol, and then baked at 280 ° C. for 1 hour in a nitrogen atmosphere to obtain vinyl polymer particles 4. The number average particle size, particle size variation coefficient (CV value) and 10% K value of the vinyl polymer particles 4 were measured. The results are shown in Table 1.
イオン交換水、メタノール、アンモニア水の量を適宜変更し、個数基準の平均粒子径が4.50μmのシード粒子を作製した後、吸収モノマーの種類と使用量を「ジビニルベンゼン(新日鐡化学社製「DVB960」:ジビニルベンゼン96%、エチルビニルベンゼン等4%含有品)500.0部」に代えて、「スチレン250部及びDVB960(新日鐡化学社製、ジビニルベンゼン含量96質量%、エチルビニルベンゼン等4%含有品)250部」に変更したこと以外は合成例4と同様にして、ビニル重合体粒子5を得た。ビニル重合体粒子5の個数平均粒子径、粒子径の変動係数(CV値)および10%K値を測定した。結果を表1に示す。 2-5. Synthesis Example 5: Synthesis of vinyl polymer particles 5 After appropriately changing the amounts of ion-exchanged water, methanol, and ammonia water to produce seed particles having a number-based average particle diameter of 4.50 μm, the types and use of absorbing monomers Instead of “divinylbenzene (“ DVB960 ”manufactured by Nippon Steel Chemical Co., Ltd .: a product containing 96% divinylbenzene, 4% ethylvinylbenzene, etc.) 500.0 parts”, “250 parts styrene and DVB960 (Nippon Steel Chemical) Vinyl polymer particles 5 were obtained in the same manner as in Synthesis Example 4 except that the product was changed to "250 parts" manufactured by the company, divinylbenzene content 96 mass%, ethylvinylbenzene 4% -containing product). The number average particle size, particle size variation coefficient (CV value) and 10% K value of the vinyl polymer particles 5 were measured. The results are shown in Table 1.
イオン交換水、メタノール、アンモニア水の量を適宜変更し、個数基準の平均粒子径が5.15μmのシード粒子を作製した後、吸収モノマーの種類と使用量を「ジビニルベンゼン(新日鐡化学社製「DVB960」:ジビニルベンゼン96%、エチルビニルベンゼン等4%含有品)500.0部」に代えて、「メチルメタクリレート475.0部、エチレングリコールジメタクリレート25.0部」に変更し、焼成の代わりに窒素雰囲気下80℃で4時間乾燥したこと以外は合成例4と同様にして、ビニル重合体粒子6を得た。ビニル重合体粒子6の個数平均粒子径、粒子径の変動係数(CV値)および10%K値を測定した。結果を表1に示す。 2-6. Synthesis Example 6: Synthesis of vinyl polymer particles 6 The amount of ion-exchanged water, methanol, and ammonia water was appropriately changed to produce seed particles having a number-based average particle size of 5.15 μm, and then the types and use of absorbing monomers. Instead of “divinylbenzene (“ DVB960 ”manufactured by Nippon Steel Chemical Co., Ltd .: a product containing 96% divinylbenzene, 4% ethylvinylbenzene, etc.) 500.0 parts”, “475.0 parts methyl methacrylate, ethylene glycol diethylenebenzene” Vinyl polymer particles 6 were obtained in the same manner as in Synthesis Example 4 except that the content was changed to “25.0 parts of methacrylate” and dried for 4 hours at 80 ° C. in a nitrogen atmosphere instead of firing. The number average particle size, particle size variation coefficient (CV value) and 10% K value of the vinyl polymer particles 6 were measured. The results are shown in Table 1.
イオン交換水、メタノール、アンモニア水の量を適宜変更し、個数基準の平均粒子径が3.25μmのシード粒子を作製した後、吸収モノマーの種類と使用量を「ジビニルベンゼン(新日鐡化学社製「DVB960」:ジビニルベンゼン96%、エチルビニルベンゼン等4%含有品)500.0部」に代えて、「n-ブチルメタクリレート1440.0部、トリエチレングリコールジメタクリレート160.0部、及びメタクリル酸400部」に変更し、焼成の代わりに窒素雰囲気下40℃で12時間乾燥したこと以外は合成例4と同様にして、ビニル重合体粒子7を得た。ビニル重合体粒子7の個数平均粒子径、粒子径の変動係数(CV値)および10%K値を測定した。結果を表1に示す。 2-7. Synthesis Example 7: Synthesis of vinyl polymer particles 7 The amount of ion-exchanged water, methanol, and ammonia water was appropriately changed to produce seed particles having a number-based average particle size of 3.25 μm, and then the types and use of absorbing monomers. In place of “divinylbenzene (“ DVB960 ”manufactured by Nippon Steel Chemical Co., Ltd .: a product containing 96% divinylbenzene, 4% ethylvinylbenzene, etc.) 500.0 parts”, the amount is 1440.0 parts n-butyl methacrylate, In the same manner as in Synthesis Example 4 except that the vinyl polymer particles 7 were changed to “160.0 parts ethylene glycol dimethacrylate and 400 parts methacrylic acid” and dried for 12 hours at 40 ° C. in a nitrogen atmosphere instead of firing. Obtained. The number average particle size, particle size variation coefficient (CV value) and 10% K value of the vinyl polymer particles 7 were measured. The results are shown in Table 1.
3-1.実施例1
上記した基材粒子(ビニル重合体粒子1)に、水酸化ナトリウム水溶液によるエッチング処理を施した後、二塩化スズ溶液に接触させ、その後、二塩化パラジウム溶液に浸漬させることにより(センシタイジング-アクチベーティング法)、パラジウム核を形成させた。パラジウム核を形成させた基材粒子10部をイオン交換水5000部に添加し、超音波照射により十分に分散させ、懸濁液を得た。この懸濁液を70℃に加熱して攪拌しながら、70℃に加熱したニッケルめっき液1000mLを添加した。前記ニッケルめっき液は、グリシンを38.0g/L、酢酸ナトリウムを57.0g/L、硫酸ニッケルを110.0g/L、次亜リン酸ナトリウムを230g/L含有しており(すなわち、ニッケルめっき液中のグリシンに対する酢酸ナトリウムの質量割合は、1.5)、pHは6.3に調整されている。液温を70℃で保持し、水素ガスの発生が停止したことを確認してから、60分間攪拌した。その後、固液分離を行い、イオン交換水、メタノールの順で洗浄することにより、ニッケルめっきを施した導電性微粒子1を得た。 3. 3. Production of conductive particles 3-1. Example 1
The above base particles (vinyl polymer particles 1) are etched with a sodium hydroxide aqueous solution, then contacted with a tin dichloride solution, and then immersed in a palladium dichloride solution (sensitizing- Activating method), palladium nuclei were formed. 10 parts of base material particles on which palladium nuclei were formed were added to 5000 parts of ion-exchanged water and sufficiently dispersed by ultrasonic irradiation to obtain a suspension. While this suspension was heated to 70 ° C. and stirred, 1000 mL of nickel plating solution heated to 70 ° C. was added. The nickel plating solution contains 38.0 g / L of glycine, 57.0 g / L of sodium acetate, 110.0 g / L of nickel sulfate, and 230 g / L of sodium hypophosphite (that is, nickel plating). The mass ratio of sodium acetate to glycine in the liquid was adjusted to 1.5), and the pH was adjusted to 6.3. The liquid temperature was maintained at 70 ° C., and after confirming that the generation of hydrogen gas was stopped, the mixture was stirred for 60 minutes. Then, solid-liquid separation was performed, and electroconductive fine particles 1 subjected to nickel plating were obtained by washing in the order of ion exchange water and methanol.
実施例1と同様にしてパラジウム核を形成させた基材粒子10部をイオン交換水5000部に添加し、超音波照射により十分に分散させ、懸濁液を得た。この懸濁液を70℃に加熱して撹拌しながら、70℃に加熱したニッケルめっき液1000mLを添加した。前記ニッケルめっき液は、グリシンを38.0g/L、リンゴ酸を10.5g/L、酢酸ナトリウムを76.0g/L、硫酸ニッケルを113.0g/L、次亜リン酸ナトリウムを230g/L含有しており(すなわち、ニッケルめっき液中のグリシンに対する酢酸ナトリウムの質量割合は、2.0)、pHは6.8に調整されている。液温を70℃で保持し、水素ガスの発生が停止したことを確認してから、60分間攪拌した。その後、固液分離を行い、イオン交換水、メタノールの順で洗浄した後、得られた導電性微粒子を、窒素(不活性)雰囲気下、280℃で2時間加熱処理を行い、ニッケルめっきを施した導電性微粒子2を得た。 3-2. Example 2
In the same manner as in Example 1, 10 parts of base particles on which palladium nuclei were formed were added to 5000 parts of ion-exchanged water and sufficiently dispersed by ultrasonic irradiation to obtain a suspension. While this suspension was heated to 70 ° C. and stirred, 1000 mL of nickel plating solution heated to 70 ° C. was added. The nickel plating solution is 38.0 g / L glycine, 10.5 g / L malic acid, 76.0 g / L sodium acetate, 113.0 g / L nickel sulfate, and 230 g / L sodium hypophosphite. It is contained (that is, the mass ratio of sodium acetate to glycine in the nickel plating solution is 2.0), and the pH is adjusted to 6.8. The liquid temperature was maintained at 70 ° C., and after confirming that the generation of hydrogen gas was stopped, the mixture was stirred for 60 minutes. Thereafter, solid-liquid separation is performed, and ion-exchanged water and methanol are washed in this order. Then, the obtained conductive fine particles are heat-treated at 280 ° C. for 2 hours in a nitrogen (inert) atmosphere to perform nickel plating. Conductive fine particles 2 were obtained.
窒素雰囲気下、280℃で2時間の加熱処理を行わないこと以外は実施例2と同様にして、導電性微粒子3を得た。
導電性微粒子3の個数平均粒子径、CV値、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子3を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線は観測されなかった。また、導電性微粒子3の1000時間経過後の耐湿熱性評価の結果は「B」であった。 3-3. Comparative Example 1
Conductive fine particles 3 were obtained in the same manner as in Example 2, except that heat treatment was not performed at 280 ° C. for 2 hours under a nitrogen atmosphere.
The number average particle diameter, CV value, nickel layer thickness, and phosphorus concentration of the conductive fine particles 3 were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 3, no diffraction lines attributed to the nickel lattice plane (200) were observed. Moreover, the result of the wet heat resistance evaluation after 1000 hours of the conductive fine particles 3 was “B”.
実施例2における窒素雰囲気下、280℃で2時間の加熱処理の代わりに、窒素雰囲気下、260℃で2時間加熱処理を行ったこと以外は実施例2と同様にして、導電性微粒子4を得た。
導電性微粒子4の個数平均粒子径、CV値、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子4を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線は観測されなかった。また、導電性微粒子4の1000時間経過後の耐湿熱性評価の結果は「B」であった。 3-4. Comparative Example 2
In the same manner as in Example 2 except that the heat treatment was performed at 260 ° C. for 2 hours in a nitrogen atmosphere instead of the heat treatment at 280 ° C. for 2 hours in the nitrogen atmosphere in Example 2, the conductive fine particles 4 were formed. Obtained.
The number average particle diameter, CV value, nickel layer thickness, and phosphorus concentration of the conductive fine particles 4 were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 4, no diffraction lines attributed to the nickel lattice plane (200) were observed. Moreover, the result of the wet heat resistance evaluation after 1000 hours of the conductive fine particles 4 was “B”.
実施例1で用いたニッケルめっき液の代わりに、乳酸52.2g/L、リンゴ酸10.0g/L、硫酸ニッケル110.0g/L、次亜リン酸ナトリウム230g/Lを含有し、pH4.6に調整されたニッケルめっき液を用いたこと以外は実施例1と同様にして、導電性微粒子5を得た。
導電性微粒子5の個数平均粒子径、CV値、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子5を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線は観測されなかった。また、導電性微粒子5の1000時間経過後の耐湿熱性評価の結果は「B」であった。 3-5. Comparative Example 3
Instead of the nickel plating solution used in Example 1, lactic acid 52.2 g / L, malic acid 10.0 g / L, nickel sulfate 110.0 g / L, sodium hypophosphite 230 g / L, pH 4. Conductive fine particles 5 were obtained in the same manner as in Example 1 except that the nickel plating solution adjusted to 6 was used.
The number average particle diameter, CV value, nickel layer thickness, and phosphorus concentration of the conductive fine particles 5 were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 5, no diffraction lines attributed to the nickel lattice plane (200) were observed. Moreover, the result of the wet heat resistance evaluation after 1000 hours of the conductive fine particles 5 was “B”.
ビニル重合体粒子1に代えて、ビニル重合体粒子2を基材粒子として用いたこと以外は、実施例2と同様にして、導電性微粒子6を得た。得られた導電性微粒子6の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子6を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-6. Example 3
Conductive fine particles 6 were obtained in the same manner as in Example 2 except that instead of the vinyl polymer particles 1, vinyl polymer particles 2 were used as base particles. The number average particle diameter of the obtained conductive fine particles 6, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 6, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
加熱処理における条件等を変更する以外は、実施例3と同様にして、導電性微粒子7を得た。得られた導電性微粒子7の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子7を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-7. Example 4
Conductive fine particles 7 were obtained in the same manner as in Example 3 except that the conditions in the heat treatment were changed. The number average particle diameter of the obtained conductive fine particles 7, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 7, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
加熱処理における条件等を変更する以外は、実施例3と同様にして、導電性微粒子8を得た。得られた導電性微粒子8の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子8を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-8. Example 5
Conductive fine particles 8 were obtained in the same manner as in Example 3 except that the conditions in the heat treatment were changed. The number average particle diameter, the thickness of the nickel layer, and the phosphorus concentration of the obtained conductive fine particles 8 were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 8, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
ビニル重合体粒子1に代えてビニル重合体粒子3を基材粒子として用いたこと以外は、実施例1と同様にして、導電性微粒子9を得た。得られた導電性微粒子9の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子9を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-9. Example 6
Conductive fine particles 9 were obtained in the same manner as in Example 1 except that the vinyl polymer particles 3 were used as base particles instead of the vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 9, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 9, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
ビニル重合体粒子1に代えてビニル重合体粒子4を基材粒子として用いたこと以外は、実施例1と同様にして、導電性微粒子10を得た。得られた導電性微粒子10の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子10を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-10. Example 7
Conductive fine particles 10 were obtained in the same manner as in Example 1 except that vinyl polymer particles 4 were used as base particles instead of vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 10, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 10, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
ビニル重合体粒子1に代えてビニル重合体粒子5を基材粒子として用いたこと以外は、実施例1と同様にして、導電性微粒子11を得た。得られた導電性微粒子11の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子11を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-11. Example 8
Conductive fine particles 11 were obtained in the same manner as in Example 1 except that the vinyl polymer particles 5 were used as base particles instead of the vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 11, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 11, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
ビニル重合体粒子1に代えてビニル重合体粒子6を基材粒子として用いたこと以外は、実施例1と同様にして、導電性微粒子12を得た。得られた導電性微粒子12の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子12を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-12. Example 9
Conductive fine particles 12 were obtained in the same manner as in Example 1 except that the vinyl polymer particles 6 were used as base particles instead of the vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 12, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 12, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
ビニル重合体粒子1に代えてビニル重合体粒子7を基材粒子として用いたこと以外は、実施例1と同様にして、導電性微粒子13を得た。得られた導電性微粒子13の個数平均粒子径、ニッケル層の膜厚、リン濃度を測定した。結果を表2に示す。導電性微粒子13を粉末X線回折測定した結果、ニッケル格子面(200)に帰属される回折線が観測され、ニッケル格子面(111)の回折線も観測された。d(200)の値、d(111)の値、d(200)/d(111)比、耐湿熱性評価の結果を後述する表3に示す。 3-13. Example 10
Conductive fine particles 13 were obtained in the same manner as in Example 1 except that vinyl polymer particles 7 were used as base particles instead of vinyl polymer particles 1. The number average particle diameter of the obtained conductive fine particles 13, the thickness of the nickel layer, and the phosphorus concentration were measured. The results are shown in Table 2. As a result of powder X-ray diffraction measurement of the conductive fine particles 13, diffraction lines attributed to the nickel lattice plane (200) were observed, and diffraction lines of the nickel lattice plane (111) were also observed. The value of d (200), the value of d (111), the d (200) / d (111) ratio, and the results of the wet heat resistance evaluation are shown in Table 3 described later.
さらに実施例3~5の対比より、基材の平均粒子径が3.0μmの導電性微粒子6~8では、d(200)/d(111)が大きい程、湿熱性条件下においても長時間にわたって抵抗値上昇を効果的に抑制できることがわかる。ニッケル層の結晶の[200]方向の成長が進行しているほど、耐湿熱性がより顕著に向上するためであると考えられる。 The conductive fine particles 3 to 5 obtained in Comparative Examples 1 to 3 are inferior in heat-and-moisture resistance when measured in 1000 hours because diffraction lines attributed to the nickel lattice plane (200) are not observed. On the other hand, since the conductive fine particles 1, 2 and 6 to 13 of Examples 1 to 10 have diffraction lines attributed to the nickel lattice plane (200), they have high heat and humidity resistance when measured in 1000 hours. Both are excellent.
Further, in comparison with Examples 3 to 5, in the conductive fine particles 6 to 8 having an average particle diameter of the base material of 3.0 μm, the larger d (200) / d (111), the longer the wet condition. It can be seen that the increase in resistance value can be effectively suppressed. It is considered that the moisture and heat resistance is more remarkably improved as the growth of the crystal of the nickel layer in the [200] direction progresses.
Claims (9)
- 基材粒子と、該基材粒子の表面を被覆する導電性金属層とを有する導電性微粒子であって、
前記導電性金属層がニッケル層を含み、
前記導電性微粒子を粉末X線回折測定したとき、ニッケルの格子面(200)に帰属される回折線が観測されることを特徴とする導電性微粒子。 Conductive fine particles having substrate particles and a conductive metal layer covering the surface of the substrate particles,
The conductive metal layer includes a nickel layer;
Conductive fine particles characterized by observing diffraction lines attributed to a lattice plane of nickel (200) when the conductive fine particles are measured by powder X-ray diffraction. - 導電性微粒子の粉末X線回折測定により測定されるニッケルの[200]方向の結晶子径をd(200)とし、ニッケルの[111]方向の結晶子径をd(111)としたとき、これらの比(d(200)/d(111))が、0.05以上である請求項1に記載の導電性微粒子。 When the crystallite diameter in the [200] direction of nickel measured by powder X-ray diffraction measurement of the conductive fine particles is d (200) and the crystallite diameter in the [111] direction of nickel is d (111), these The conductive fine particles according to claim 1, wherein the ratio (d (200) / d (111)) is 0.05 or more.
- 前記基材粒子がビニル重合体粒子である請求項1又は2に記載の導電性微粒子。 The conductive fine particles according to claim 1 or 2, wherein the substrate particles are vinyl polymer particles.
- 前記基材粒子の個数平均粒子径が1μm以上、50μm以下である請求項1~3のいずれかに記載の導電性微粒子。 The conductive fine particles according to any one of claims 1 to 3, wherein the base particles have a number average particle diameter of 1 µm or more and 50 µm or less.
- 前記基材粒子の10%K値が100N/mm2以上、40000N/mm2以下である請求項1~4のいずれかに記載の導電性微粒子。 10% K value of the base particle is 100 N / mm 2 or more, the conductive particle according to any one of claims 1 to 4 is 40000N / mm 2 or less.
- 前記基材粒子の個数平均粒子径が3μm以下であり、かつ、10%K値が4000N/mm2超である請求項1~5のいずれかに記載の導電性微粒子。 The conductive fine particles according to any one of claims 1 to 5, wherein the base particles have a number average particle diameter of 3 µm or less and a 10% K value of more than 4000 N / mm 2 .
- 前記基材粒子の個数平均粒子径が3μm以下であり、かつ、導電性微粒子の粉末X線回折測定により測定されるニッケルの[200]方向の結晶子径d(200)と、ニッケルの[111]方向の結晶子径d(111)の比(d(200)/d(111))が0.2以上である請求項1~5のいずれかに記載の導電性微粒子。 The number average particle diameter of the substrate particles is 3 μm or less, and the crystallite diameter d (200) in the [200] direction of nickel measured by powder X-ray diffraction measurement of the conductive fine particles, and [111] of nickel 6. The conductive fine particle according to claim 1, wherein the ratio (d (200) / d (111)) of the crystallite diameter d (111) in the direction is 0.2 or more.
- 前記基材粒子の10%K値が100N/mm2以上、4000N/mm2以下である請求項1~5のいずれかに記載の導電性微粒子。 10% K value of the base particle is 100 N / mm 2 or more, the conductive particle according to any one of claims 1 to 5, is 4000 N / mm 2 or less.
- 請求項1~8のいずれかに記載の導電性微粒子を含む異方性導電材料。 An anisotropic conductive material comprising the conductive fine particles according to any one of claims 1 to 8.
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