WO2015141716A1 - 樹脂粒子、導電性微粒子及びそれを用いた異方性導電材料 - Google Patents
樹脂粒子、導電性微粒子及びそれを用いた異方性導電材料 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1676—Heating of the solution
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
Definitions
- the present invention relates to resin particles having convex portions, conductive fine particles having protrusions, and an anisotropic conductive material using the same.
- resin particles having protrusions are resin additives (anti-blocking agents, light diffusing agents, etc.), matting agents, toner additives, powder paints, water-dispersed paints, decorative board additives, artificial marble. It is applied to a wide range of applications such as additives for cosmetics, fillers for cosmetics, column fillers for chromatography, and substrates for conductive fine particles.
- the resin particles used in these applications (particularly resin particles used as resin additives and conductive fine particle substrates) have a uniform protrusion size and protrusion distribution density, and the protrusions are detached from the resin particles. It is desirable that it is difficult.
- the resin particles having protrusions have a uniform protrusion size and protrusion distribution density, and that the protrusions are not easily detached.
- Patent Document 1 proposes resin particles obtained by suspension polymerization of a vinyl monomer and a non-crosslinked acrylic polymer in the presence of a surfactant that is a non-reactive phosphate compound. Further, in Patent Document 2, by attaching functional groups having reactivity to two kinds of particle surfaces having different particle diameters, small particle diameter particles are bonded to the large particle diameter particle surfaces by chemical bonds. Uneven particles have been proposed. Further, Patent Document 3 proposes silicone fine particles in which granular polyorganosilsesquioxane is generated by condensation of organotrialkoxysilane and adhered to the surface of silicone elastomer spherical fine particles.
- An anisotropic conductive material is a material in which conductive fine particles are dispersed in a binder resin or the like.
- anisotropic conductive paste ACP
- anisotropic conductive film ACF
- anisotropic conductive ink anisotropic conductive
- the conductive fine particles used for this anisotropic conductive material those obtained by coating the surface of resin particles as a substrate with a conductive metal layer in addition to metal particles are used.
- the conductive fine particles composed of the resin particles and the conductive metal layer are electrically connected between electrodes and wirings by a conductive metal layer formed on the surface.
- Patent Document 4 describes a method of forming microprotrusions at the same time when a nickel or nickel alloy film is formed on the surface of spherical core particles by an electroless plating method.
- this method uses abnormal deposition of plating, and it was necessary to control the electroless plating conditions to a special condition in order to form microprotrusions, so the shape of microprotrusions is controlled within a certain range.
- Patent Document 5 describes a method of forming protrusions by adsorbing non-conductive inorganic particles to a plastic core and forming a metal plating layer. In this method, the plastic core and When the adsorption power of the non-conductive inorganic particles is not sufficient, the protrusions are likely to drop off, and sufficient connection reliability may not be ensured.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide resin particles in which the size of the protrusions and the distribution density of the protrusions are uniform and the protrusions are not easily detached. Moreover, this invention makes it a subject to provide the electroconductive fine particles which can suppress isolation
- a material for forming a protruding portion is used for controlling the protrusion (convex portion) shape (size, distribution density). It is important that the material is different from the material forming the particle part (spherical part).
- the part including the protrusion (periphery part having the convex part) and the particle part was found to be important that the center of curvature is present in the spherical part, and the present invention was completed.
- the resin particle according to the present invention is a resin particle composed of a spherical part and a peripheral part having a plurality of convex parts formed on the surface thereof, and the spherical part and the peripheral part are a vinyl polymer and And / or the composition of the spherical portion and the peripheral portion is different, the melting point of the peripheral portion is 200 ° C. or higher, and the peripheral portion when the cross section of the resin particle is observed with a transmission electron microscope The center of curvature of the boundary line between the spherical portions is present in the spherical portion.
- the average height of the protrusions is 0.05 ⁇ m or more and 5 ⁇ m or less, and the average bottom diameter of the protrusions is 0.1 ⁇ m or more and 10 ⁇ m or less.
- the number density of protrusions is preferably 0.01 / ⁇ m 2 or more and 10 / ⁇ m 2 or less, and the number of protrusions per resin particle is 5 or more.
- the number is preferably 5000 or less.
- the resin particles of the present invention preferably have a volume average particle diameter of 1 ⁇ m or more and 50 ⁇ m or less.
- the resin particles of the present invention preferably have an average contact angle of the convex portions of 90 ° or less.
- the resin particles of the present invention preferably have a core-shell structure composed of a core and a shell, and the shell preferably includes the peripheral edge.
- the present inventors have found that by using resin particles having specific convex portions as base particles, it is possible to form conductive fine particles in which protrusion detachment is suppressed regardless of plating conditions. completed. That is, the conductive fine particles of the present invention have the resin particles and a conductive metal layer that covers the surface convex portions of the resin particles along the shape of the convex portions, and the anisotropic fine particles containing the conductive fine particles. Conductive conductive materials are also included in the technical scope of the present invention.
- the resin particles according to the present invention are resin particles composed of a spherical portion and a peripheral portion having a plurality of convex portions formed on the surface thereof, wherein the spherical portion and the peripheral portion are a vinyl polymer and / or
- the spherical part and the peripheral part are formed of a polysiloxane component, the composition of the spherical part is different from that of the peripheral part, the melting point of the peripheral part is 200 ° C.
- the conductive fine particles of the present invention use resin particles having specific convex portions as the base particles, the shape of the protrusions on the surface of the conductive fine particles can be controlled, and the separation of the protrusions is suppressed. .
- FIG. 1 (a) and 1 (b) are schematic views of protrusions on the cross section of the resin particle of the present invention.
- 2 (a) and 2 (b) are schematic views of protrusions on the cross section of the resin particle of the present invention. It is a figure for demonstrating the height and base (diameter) of a convex part.
- 3 (a) and 3 (b) are schematic views of protrusions on the cross section of the resin particle of the present invention. It is a figure for demonstrating the contact angle of a convex part.
- FIG. 4 is a scanning electron micrograph (magnification: 4,000 times) of the resin particles of Production Example 1.
- FIG. 5 is a scanning electron micrograph (magnification 3,500 times) of the resin particles of Production Example 2.
- FIG. 4 is a scanning electron micrograph (magnification: 4,000 times) of the resin particles of Production Example 1.
- FIG. 5 is a scanning electron micrograph (magnification 3,500 times) of the resin particles of Production Example
- FIG. 6 is a scanning electron micrograph (magnification: 3,000 times) of the resin particles of Production Example 3.
- FIG. 7 is a scanning electron micrograph (magnification 3,700 times) of the resin particles of Production Example 8.
- FIG. 8 is a transmission electron micrograph (magnification 10,000 times) of the cross section of the resin particle of Production Example 3.
- FIG. 9 is a transmission electron micrograph (magnification of 5,000 times) of the cross section of the resin particle of Production Example 8.
- 10 is a scanning electron micrograph (magnification 3,500 times) of the conductive fine particles of Example 2.
- FIG. 7 is a scanning electron micrograph (magnification 3,700 times) of the resin particles of Production Example 8.
- FIG. 8 is a transmission electron micrograph (magnification 10,000 times) of the cross section of the resin particle of Production Example 3.
- FIG. 9 is a transmission electron micrograph (magnification of 5,000 times) of the cross section of the resin particle of Production Example 8.
- 10 is a scanning electron micrograph (magnification 3,500
- the resin particle of the present invention is composed of a spherical portion and a peripheral portion having a plurality of convex portions formed on the surface thereof, and the peripheral portion is formed on the surface of the spherical portion. Is surrounded by the peripheral edge. And a peripheral part has the said some convex part. Furthermore, the center of curvature of the boundary line between the peripheral portion and the spherical portion when the cross section of the resin particle of the present invention is observed with a scanning transmission electron microscope exists in the spherical portion. Thereby, a convex part becomes difficult to detach
- FIG. 1 (a) and 1 (b) are schematic views of protrusions on the cross section of the resin particle of the present invention.
- the peripheral part (2a) which has a convex part (3) exists in the surface of a spherical part (1)
- the boundary line (10) has the center of curvature in the spherical portion (1).
- the fact that the center of curvature of the boundary line (10) exists in the spherical part (1) means that the boundary line (10) is convex toward the peripheral part side.
- the peripheral part (2a) may be comprised by the peripheral layer (2b) and the convex part (3).
- the said peripheral part (2a) does not have a peripheral layer (2b) (namely, the thickness of a peripheral layer (2b) is 0 micrometer), and may be comprised only by a convex part (3). Good. Even in such a case, as shown in FIG. 1B, the peripheral portion (2a) having the convex portion (3) is present on the surface of the spherical portion (1), and the spherical portion (1) and the peripheral portion
- the boundary line (10) between the parts (2a) has a center of curvature in the spherical part (1).
- the spherical portion alone is preferably a spherical shape having no protrusion, and more preferably a true spherical shape.
- the fact that the center of curvature of the boundary line between the peripheral part and the spherical part in the resin particle cross section exists in the spherical part means that the boundary line is a straight line or a curve, and the curvature is directed to the peripheral part side (to the outside).
- the curvature of the curve is defined as the radius of the contact circle of the curve (curvature radius), the curvature radius of the boundary line between the peripheral portion and the spherical portion, and the change rate of the radius of the spherical portion (curvature radius ⁇
- the absolute value of the radius of the spherical part) / the radius of the spherical part) is preferably within 10%, more preferably within 5%.
- the resin particle may be subjected to compressive stress. Even if the spherical part is a perfect sphere, Sometimes not.
- the convex portion means a product of height ( ⁇ m) and base diameter ( ⁇ m), that is, height ⁇ base diameter ( ⁇ m 2 ) of 0.001 ( ⁇ m 2 ) or more.
- the product of the height and the base diameter is more preferably 0.005 ( ⁇ m 2 ) or more, and still more preferably 0.009 ( ⁇ m 2 ) or more.
- an upper limit is not specifically limited, Usually, it is 50 (micrometer ⁇ 2 >) or less.
- the average height of the convex portions is preferably 0.05 ⁇ m or more and 5 ⁇ m or less.
- the average bottom diameter of the convex portions is preferably 0.10 ⁇ m or more and 10 ⁇ m or less. More preferably, it is 0.12 micrometer or more, More preferably, it is 0.15 micrometer or more.
- the larger the average base diameter of the convex portion the larger the contact area between the spherical portion and the convex portion, so that the convex portion is less likely to be detached.
- the smaller the average base diameter of the protrusions the more effective the effects of the protrusions (light diffusion improvement effect, blocking resistance improvement effect, connection stability improvement effect, etc.) even when the particle size of the resin particles is reduced. Can be demonstrated. Therefore, it is more preferably 9.0 ⁇ m or less, and still more preferably 8.0 ⁇ m or less.
- the resin particles of the present invention preferably have a ratio (height / bottom diameter) of the average height of the protrusions to the average base diameter (height / base diameter) of 0.10 or more and 0.80 or less.
- the ratio (height / base diameter) is small, the protrusions are more difficult to be detached. Therefore, it is more preferably 0.70 or less, and still more preferably 0.60 or less.
- the ratio of the average height of the protrusions to the volume average particle diameter of the resin particles is 0.001 or more and 0.20 or less.
- the ratio (average height of convex portions / volume average particle diameter) is small, the detachment of the protrusions is further suppressed. Therefore, it is more preferably 0.19 or less, and still more preferably 0.18 or less.
- the average height and average base diameter of the convex portions can be measured based on a scanning electron micrograph taken at a magnification of 10,000 times or more. Specifically, the resin particles were photographed with a scanning electron microscope at a magnification of 10,000 times or more, and in the obtained scanning electron micrographs, as shown in FIGS. 2 (a) and 2 (b), the periphery of the resin particles A triangle (4) having a line segment connecting two starting points (6a, 6b) of the convex part (3) existing in the part (2a) as a base, and a top part (8) of the convex part (3) as a vertex. Draw.
- the base (5) of the triangle (4) is defined as the base of the convex portion (3), and the height of the triangle (4) is defined as the height of the convex portion (3). Furthermore, about 50 or more convex parts of the resin particle, the height and the base diameter are measured by the above-described method, and averaged to obtain the average height and the average base diameter of the convex part of each resin particle, respectively.
- the number of convex portions per resin particle is preferably 5 or more and 5000 or less.
- the contact area of a convex part and a spherical part can be enlarged, so that the number of convex parts per resin particle is small, detachment
- the number of convex portions per resin particle can be measured based on a scanning electron micrograph taken at a magnification of 3000 times or more. Specifically, for each resin particle, the number of protrusions present on the observation surface side of the scanning electron micrograph is doubled to be the number of protrusions per resin particle. For the five resin particles per resin particle, the number of convex portions is measured by the method described above, and the average is taken as the number of convex portions per resin particle.
- the coefficient of variation of the number of convex portions per resin particle can be, for example, 20% or less, preferably 18% or less, more preferably 15% or less, and can suppress variation between resin particles. Performance can be made uniform.
- the coefficient of variation is usually preferably 0.1% or more, more preferably 1% or more, and further preferably 2% or more.
- the convex portions can be uniformly formed on the surface of the resin particles, and the performance of the conductive fine particles can be made uniform.
- the resin particles are divided into four sections by drawing two straight lines that pass through the center of the resin particles and are orthogonal to each other at the particle center.
- Dividing and calculating the standard deviation of the number of convex parts per section for one resin particle, and dividing this standard deviation by the number of convex parts per resin particle, the average value is For example, it can be 10% or less, preferably 8% or less, more preferably 7% or less.
- the average value is usually preferably 0.01% or more, more preferably 0.1% or more, and further preferably 0.2% or more.
- the resin particles of the present invention preferably have a convex number density of 0.01 / ⁇ m 2 or more and 10 / ⁇ m 2 or less.
- the contact area of a convex part and a spherical part can be enlarged, so that the number density of a convex part is small, detachment
- the number density of the convex portions means the number of convex portions existing per 1 ⁇ m 2 of the area of the spherical portion or the peripheral layer.
- the number density of convex portions in the resin particles can be calculated based on the radius of the spherical portion or the sum of the radius of the spherical portion and the thickness of the peripheral layer and the number of convex portions per resin particle. Specifically, using a scanning electron micrograph taken at a magnification of 10,000 or more, use the caliper diameter calculation tool attached to the device to calculate the diameter of the spherical part or the diameter including the spherical part and the peripheral layer.
- the number of protrusions per resin particle is the surface area of the spherical part (4 ⁇ ⁇ ⁇ square of the radius of the spherical part) or the surface area of the peripheral layer (4 ⁇ ⁇ ⁇ (the radius of the spherical part and the thickness of the peripheral layer). It can be calculated by dividing by the square of the sum).
- the contact angle of the protrusions is preferably 90 ° or less on average.
- the lower limit of the contact angle is not particularly limited, but as the contact angle is larger, the height of the convex portion can be increased, and the effect by the convex portion (light diffusion ability improving effect, blocking resistance improving effect, connection stability improving)
- the angle is preferably 5 ° or more, more preferably 10 ° or more, and further preferably 15 ° or more.
- the contact angle is large, when used as a base material for conductive fine particles, the effect of improving the connection stability by the convex portion can be more effectively exhibited. More preferably, it is 35 ° or more, and further preferably 45 ° or more.
- the contact angle when the convex portion is assumed to be a droplet with respect to the peripheral layer or the spherical portion can be defined as an angle formed by the tangent of the peripheral layer or the spherical portion and the tangent of the convex portion at the starting point of the convex portion, It can be measured based on a transmission electron micrograph taken at a magnification of 10,000 or more.
- the peripheral edge may be composed of a convex part and a peripheral layer.
- the thickness of the peripheral layer is not particularly limited, but when observed with a transmission electron microscope, for example, it is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably. 1 ⁇ m or less.
- the lower limit of the thickness of the peripheral layer may preferably be 0 ⁇ m.
- the peripheral portion if the thickness of the peripheral portion is the sum of the average height of the convex portions and the thickness of the peripheral layer, the peripheral portion preferably has a thickness of 10 ⁇ m or less, more preferably 9 ⁇ m or less, and even more preferably. 8 ⁇ m or less. Moreover, it is preferable that the thickness of a peripheral part is 0.10 micrometer or more, More preferably, it is 0.11 micrometer or more, More preferably, it is 0.12 micrometer or more.
- the ratio of the average height of the convex portion to the thickness of the peripheral portion is, for example, preferably 0.5 or more, more preferably 0.7 or more, Preferably it is 0.8 or more, Especially preferably, it is 0.9 or more.
- the maximum value of the ratio (average height of convex portions / thickness of peripheral edge portion) may be preferably 1.
- the ratio of the thickness of the peripheral part to the volume average particle diameter of the resin particles is preferably 0.001 or more, more preferably 0.005 or more, and still more preferably. 0.01 or more.
- the ratio (peripheral thickness / volume average particle diameter) is preferably 0.40 or less, more preferably 0.38 or less, and still more preferably 0.36 or less.
- the resin particles of the present invention have a melting point of the peripheral portion of 200 ° C. or higher.
- the melting point of the peripheral portion is preferably 220 ° C. or higher, more preferably 240 ° C. or higher, and further preferably 250 ° C. or higher.
- fusing point is not specifically limited, For example, it is 400 degreeC.
- the melting point of the peripheral edge can be measured as the temperature at which the peripheral edge is deformed by heating.
- the peripheral portion in the resin particle of the present invention is formed of a vinyl polymer and / or a polysiloxane component, and the melting points of the vinyl polymer and / or the polysiloxane component constituting the peripheral portion are each 200 ° C. or higher. It is preferable from the viewpoint that the melting point of the peripheral portion can be easily set to 250 ° C. and the hardness of the convex portion at room temperature (25 ° C.) can be improved.
- the melting point of the component constituting the peripheral portion (vinyl polymer and / or polysiloxane component) is more preferably 220 ° C. or higher, further preferably 240 ° C. or higher, more preferably 250 ° C. or higher.
- fusing point is not specifically limited, For example, it is 400 degreeC.
- the resin particles of the present invention preferably have a core-shell structure composed of a core and a shell, wherein the core includes a spherical portion and the shell includes a peripheral portion having a convex portion.
- the peripheral portion having the convex portion is formed only by the shell, and in such a resin particle, the spherical portion is configured by only the core, and the peripheral portion having the convex portion is configured by only the shell,
- a spherical part is comprised by a part of core and shell, and the peripheral part which has a convex part is comprised only by a shell.
- the resin particles of the present invention preferably have a volume average particle diameter of 1 ⁇ m or more and 50 ⁇ m or less. More preferably, they are 1.5 micrometers or more and 40 micrometers or less, More preferably, they are 2 micrometers or more and 35 micrometers or less, Most preferably, they are 2.5 micrometers or more and 30 micrometers or less.
- the volume average particle diameter of the resin particles is within the above range, additives for resins (anti-blocking agents, light diffusing agents, etc.), matting agents, additives for toners, powder paints, water-dispersed paints, decorative panels It can be suitably used as an additive, an additive for artificial marble, a filler for cosmetics, a column filler for chromatography, a substrate for conductive fine particles, and the like.
- the “volume average particle diameter” in the present invention is a value measured by a precision particle size distribution measuring apparatus using the Coulter principle (for example, trade name “Coulter Multisizer III type”, manufactured by Beckman Coulter, Inc.). To do.
- the transmission electron microscope detects light transmitted and scattered by irradiating a sample with an electron beam.
- a bright field signal transmission signal in a range including a scattering angle of 0
- the difference in density inside the sample can be expressed by the difference in light and dark
- a dark field signal a transmission signal in a scattering angle range in which the scattering angle does not include 0 (greater than the bright field signal)
- the difference between the atomic weights of the contained elements can be expressed by the difference between light and dark.
- transmission electron microscopy that detects dark field signals is preferred.
- a difference in brightness occurs due to a difference between the atomic weight of an element included in a specific region and the atomic weight of an element included in the surrounding region, and a boundary line can be observed.
- the larger the atomic weight of the element the lower the brightness, and the darker the region containing relatively high atomic weight elements such as silicon, phosphorus and sulfur.
- the larger the atomic weight the higher the brightness can be displayed, and it is only necessary to observe the boundary line derived from the difference in the atomic weight of the element.
- a similar cross-sectional image can be obtained by using a scanning transmission electron microscope instead of the transmission electron microscope.
- the resin particles of the present invention are formed of a vinyl polymer and / or a polysiloxane component, and more preferably formed of a vinyl polymer and a polysiloxane component.
- the vinyl polymer means a polymer having a vinyl polymer skeleton and can be formed by polymerizing (preferably radical polymerization) a vinyl monomer (vinyl group-containing monomer).
- a polysiloxane component (also referred to as a polysiloxane skeleton) means a component having a siloxane bond (Si—O—Si) and can be formed by polymerizing a silane monomer.
- the polysiloxane component is preferably a polysiloxane component formed using a silane crosslinkable monomer (preferably a silane crosslinkable monomer of the third form, more preferably a silane monomer having a vinyl group). .
- the spherical portion and the peripheral portion are both formed of a vinyl polymer and / or a polysiloxane component, but the composition of the spherical portion and the peripheral portion is different.
- the composition of the spherical part and the peripheral part is expressed by the type and mass ratio of each monomer forming the spherical part and the peripheral part.
- the composition of the vinyl polymer and the polysiloxane component is the vinyl weight. It is expressed by the type and mass ratio of each monomer forming the coalescence and polysiloxane component.
- the vinyl polymer constituting the spherical portion and the vinyl polymer constituting the peripheral portion have different compositions
- the polysiloxane component constituting the spherical portion and the polysiloxane component constituting the peripheral portion are An embodiment in which the composition of at least one of the vinyl polymer and the polysiloxane component constituting the spherical portion and the peripheral portion is different as in the case of different compositions;
- the vinyl polymer and the poly in the spherical portion and the peripheral portion A mode in which the content of at least one of the siloxane components (mass ratio in the spherical portion or the peripheral portion) is different; the vinyl polymer contained in the spherical portion and the peripheral portion, and the number other than the polysiloxane component
- composition of at least one of the vinyl polymer and the polysiloxane component constituting the spherical part and the peripheral part is different; the vinyl polymer in the spherical part and the peripheral part and at least one of the polysiloxane component is different.
- content mass ratio in a spherical part or a peripheral part
- composition of the said vinyl polymer and a polysiloxane component differs, the case where any one of a spherical part and a peripheral part does not contain a vinyl polymer or a polysiloxane component is also included.
- the composition of the core part contained in a spherical part and the shell part containing a peripheral part differ.
- the vinyl polymer or polysiloxane component constituting the core portion and the vinyl polymer or polysiloxane component constituting the shell portion are different in composition, at least the vinyl polymer and the polysiloxane component in the core portion and the shell portion
- the aspect etc. from which any one content (mass ratio) differs are mentioned preferably.
- the size (height, base diameter) of the convex part and the dispersion density of the convex part can be adjusted.
- the component which forms a spherical part contains a vinyl polymer at least, and it is more preferable that a vinyl polymer and a polysiloxane component are included.
- the component forming the peripheral portion preferably includes at least a polysiloxane component, and more preferably includes a vinyl polymer and a polysiloxane component.
- the component forming the core part preferably contains at least a vinyl polymer, and more preferably contains a vinyl polymer and a polysiloxane component.
- the component forming the shell part preferably includes at least a polysiloxane component, and more preferably includes a vinyl polymer and a polysiloxane component.
- the “vinyl group” includes not only a carbon-carbon double bond (ethenyl group) but also a (meth) acryloxy group, an allyl group, an isopropenyl group, a vinylphenyl group, an isopropenylphenyl group, Also included are substituents composed of functional groups and polymerizable carbon-carbon double bonds.
- substituents composed of functional groups and polymerizable carbon-carbon double bonds are “(meth) acryloxy group”, “(meth) acrylate”, and “(meth) acryl” are “acryloxy group and / or methacryloxy group”, “acrylate and / or methacrylate”, “acrylic”. And / or “methacryl”.
- the vinyl monomer forming the vinyl polymer is classified into a vinyl crosslinkable monomer and a vinyl non-crosslinkable monomer.
- the vinyl crosslinkable monomer has a vinyl group and can form a crosslinked structure, and specifically, a monomer having two or more vinyl groups in one molecule (monomer ( 1)), or a monomer having one vinyl group and a binding functional group other than a vinyl group (carboxyl group, protic hydrogen-containing group such as hydroxy group, terminal functional group such as alkoxy group, etc.) in one molecule Body (monomer (2)).
- monomer (2) monomer having two or more vinyl groups in one molecule
- a counterpart monomer capable of reacting (binding) with a binding functional group other than the vinyl group of the monomer (2) it is necessary to have a counterpart monomer capable of reacting (binding) with a binding functional group other than the vinyl group of the monomer (2). .
- Examples of the monomer (1) (monomer having two or more vinyl groups in one molecule) among the vinyl crosslinkable monomers include, for example, allyl (meth) such as allyl (meth) acrylate.
- (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 having two or more (meth) acryloyl groups in one molecule are particularly preferable.
- (meth) acrylates having 3 or more (meth) acryloyl groups in one molecule are particularly preferred, and among them, acrylates having 3 or more acryloyl groups in one molecule are preferred.
- the styrenic polyfunctional monomers monomers having two vinyl groups in one molecule such as divinylbenzene are preferable.
- a monomer (1) may be used independently and may use 2 or more types together.
- the monomer (2) (monomer having one vinyl group and a binding functional group other than vinyl group in one molecule) is, for example, (meth) acrylic Monomers having a carboxy group such as 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; containing alkoxy groups such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 2-butoxyethyl (meth) acrylate Alkoxy groups such as (meth) acrylates and alkoxystyrenes such as p-methoxystyrene Monomer; and the like.
- a monomer (2) may be used independently and may use 2 or more types
- vinyl non-crosslinkable monomer 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) (a monomer having one vinyl group in one molecule) includes a (meth) acrylate monofunctional monomer and a styrene monofunctional monomer. Is included.
- 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, pt-butyl styrene, o-chlorostyrene, m-chloro Examples include styrenes containing halogen groups such as styrene 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 an embodiment containing at least the vinyl crosslinkable monomer (1) is preferable.
- the vinyl crosslinkable monomer (1) and the vinyl non-crosslinkable monomer (3) are included.
- An embodiment in particular, a copolymer of the monomer (1) and the monomer (3) is preferable.
- the resin particles of the present invention preferably contain 20% by mass or more of vinyl polymer in 100% by mass of resin particles, more preferably 30% by mass or more, still more preferably 50% by mass or more, and still more preferably 60% by mass. As mentioned above, 70 mass% or more is included especially preferably.
- the upper limit of the content ratio of the vinyl polymer is 100% by mass.
- the polysiloxane component can be formed by using a silane monomer, which is divided into a silane crosslinkable monomer and a silane non-crosslinkable monomer.
- 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 one that cross-links the vinyl polymer skeleton and the vinyl polymer skeleton (first form); one that cross-links the polysiloxane skeleton and polysiloxane skeleton (first A second form); a substance that cross-links a vinyl polymer skeleton and a polysiloxane skeleton (third form).
- silane crosslinkable monomer capable of forming the first form include silane compounds having two or more vinyl groups such as dimethyldivinylsilane, methyltrivinylsilane, and tetravinylsilane. It is done.
- silane crosslinkable monomer that can form the second form include tetrafunctional silane monomers such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane.
- a trifunctional silane monomer such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane;
- silane crosslinkable monomer capable of forming the third form (crosslinking between vinyl polymer and polysiloxane) include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acrylonitrile.
- (Meth) acryloyl groups such as loxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxyethoxypropyltrimethoxysilane Di- or trialkoxysilanes having a vinyl group (ethenyl group) such as vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, etc .; 3-glycidoxypropyltrimeth Di- or trialkoxysilanes having an epoxy group such as silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyl And di- or trial
- silane non-crosslinkable monomer examples include bifunctional silane monomers such as dialkyl silane such as dimethyldimethoxysilane and dimethyldiethoxysilane; monofunctional such as trialkylsilane such as trimethylmethoxysilane and trimethylethoxysilane. Silane monomer and the like. 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 radically polymerizable vinyl group (for example, a vinyl group such as a carbon-carbon double bond or a (meth) acryloyl group).
- the polysiloxane skeleton is a silane crosslinkable monomer (preferably having a vinyl group, more preferably vinyl having the ability to form at least the third form (crosslinking between vinyl polymer and polysiloxane) as a constituent component.
- a polysiloxane skeleton is preferable.
- the amount of vinyl monomer used is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 100 parts by mass of the silane monomer.
- it is 10 mass parts or more, 5000 mass parts or less are preferable, More preferably, it is 4000 mass parts or less, More preferably, it is 3000 mass parts or less.
- the monomer component for forming the resin particles of the present invention preferably contains a crosslinkable monomer such as a vinyl crosslinkable monomer or a silane crosslinkable monomer.
- a crosslinkable monomer such as a vinyl crosslinkable monomer or a silane crosslinkable monomer.
- the proportion of the crosslinkable monomer (total of the vinyl crosslinkable monomer and the silane crosslinkable monomer) in the total monomers forming the vinyl polymer particles is determined by the light diffusion ability, elastic deformation, and restoration. From the point of being excellent in force and the like, 1% by mass or more is preferable, more preferably 2% by mass or more, and further preferably 5% by mass or more.
- the ratio of the crosslinkable monomer is within the above range, the light diffusing ability and restoring force can be improved while maintaining excellent elastic deformation characteristics.
- the upper limit of the ratio of the crosslinkable monomer is not particularly limited, but depending on the type of the crosslinkable monomer used, if the ratio of the crosslinkable monomer is too large, it may become too hard to be elastically deformed. . Therefore, the proportion of the crosslinkable monomer is preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 93% by mass or less, still more preferably 90% by mass or less, and particularly preferably 85% by mass. % Or less.
- the resin particles of the present invention may contain other components to the extent that the properties of the vinyl polymer and / or polysiloxane component are not impaired.
- the resin particles preferably contain 85% by mass or more of the vinyl polymer and / or polysiloxane component, more preferably 95% by mass or more, and still more preferably 98% by mass or more.
- the resin particles of the present invention are: Step (a): A step of polymerizing a core monomer composition containing a vinyl monomer and / or a silane monomer as a polymerization component to form core particles, Step (b): A step of obtaining a resin particle 1 by coating a surface of the core particle with a silane monomer composition containing a silane monomer as a polymerization component to form a shell, It can manufacture with the manufacturing method containing.
- the manufacturing method further includes: Step (c): The resin particles 1 obtained in the step (b) are absorbed with a vinyl monomer composition for shell containing a vinyl monomer as a polymerization component, and then polymerized to obtain resin particles 2. It is preferable to include a process.
- the core of the resin particle of the present invention can be produced by polymerizing the monomer composition for core containing the monomer as a polymerization component. .
- the mechanical properties and optical properties of the resin particles can be adjusted by the monomers used in the core monomer composition.
- the “monomer composition” means a composition composed only of monomers. However, the polymerization of the core monomer composition is usually carried out in a state where a catalyst component such as a polymerization initiator coexists with the composition.
- the core monomer composition comprises a vinyl monomer selected from the above monomers (hereinafter referred to as “core vinyl monomer”) and / or a silane monomer (hereinafter referred to as “core silane monomer”). It is preferable to include at least a vinyl monomer for the core.
- a vinyl monomer for the core among the vinyl monomers exemplified above, a monomer having two or more vinyl groups (1), a monomer having a vinyl group and other functional groups (2 ) And a monomer (3) having one vinyl group.
- One vinyl monomer may be used alone, or two or more vinyl monomers may be used. From the viewpoint of adjusting mechanical properties, optical properties, and the like, it is preferable to use two or more types.
- the monomer (1) having two or more vinyl groups di (meth) acrylates and aromatic hydrocarbon crosslinking agents are preferable, and as the monomer (3) having one vinyl group, Alkyl (meth) acrylates, cycloalkyl methacrylates, and styrene monofunctional monomers are preferred.
- the core monomer composition preferably includes a monomer (2) containing a vinyl group and other functional groups as the vinyl monomer for the core.
- a monomer (2) containing a vinyl group and other functional groups as the vinyl monomer for the core.
- the monomers (2) It is preferable to include a monomer having a hydrophilic group such as a carboxy group, a hydroxy group, an amino group, or a thiol group and a vinyl group. Thereby, the adjustment of the solubility parameter mentioned later becomes easy and it becomes easier to form a convex part.
- the ratio of the core vinyl monomer is 10% in the total of 100% by mass of the core vinyl monomer and the core silane monomer. It is preferably at least 20% by mass, more preferably at least 20% by mass, even more preferably at least 30% by mass, even more preferably at least 60% by mass, even more preferably at least 70% by mass, particularly preferably at least 80% by mass. It is. The upper limit is 100% by mass.
- the core monomer composition includes the core silane monomer, the content of the core vinyl monomer is 0.3 parts by mass or more with respect to 1 part by mass of the core silane monomer.
- it is 0.5 parts by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more. Moreover, it is preferable that it is 50 mass parts or less with respect to 1 mass part of silane monomers for cores, More preferably, it is 40 mass parts or less, More preferably, it is 30 mass parts or less.
- the ratio of the core vinyl monomer is preferably less than 60% by mass, more preferably 55% by mass or less, out of the total of 100% by mass of the core vinyl monomer and the core silane monomer. Yes, preferably 10% by mass or more, more preferably 20% by mass or more.
- the amount of the vinyl monomer for the core is preferably less than 2 parts by mass, more preferably 1.5 parts by mass or less, and still more preferably 1. with respect to 1 part by mass of the silane monomer for the core. 2 parts by mass or less, preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. When the ratio of the vinyl monomer for the core is within this range, it is particularly easy to obtain core particles having a small particle size.
- silane crosslinkable monomer for cores, a silane crosslinkable monomer can be preferably used, and a silane crosslinkable monomer (third form) capable of forming an organic polymer skeleton and a polysiloxane skeleton is used. More preferably, it can be used.
- the core monomer composition may contain a monomer other than the core vinyl monomer and the core silane monomer, but the core vinyl monomer, or the core vinyl. It is preferable that the monomer and the core silane monomer are the main components. Specifically, in the core monomer composition 100% by mass, the core vinyl monomer and the core silane monomer The total mass ratio is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 98% by mass or more, and particularly preferably 100% by mass.
- the core monomer composition preferably has a solubility parameter of 8 (cal / cm 3 ) 1/2 or more, and preferably 11 (cal / cm 3 ) 1/2 or less.
- the solubility parameter of the core monomer composition is more preferably 8.5 (cal / cm 3 ) 1/2 or more, further preferably 8.9 (cal / cm 3 ) 1/2 or more, and particularly preferably 9 .1 (cal / cm 3 ) 1/2 or more.
- the solubility parameter of the core monomer composition is more preferably 10.5 (cal / cm 3 ) 1/2 or less, and even more preferably 10 (cal / cm 3 ) 1/2 or less. The higher the solubility parameter, the higher the hydrophilicity of the core monomer composition, and the lower the solubility parameter, the higher the hydrophobicity of the core monomer composition.
- the solubility parameter represents the solubility parameter obtained by the Fedors method.
- the solubility parameter of the monomer can be directly calculated.
- the solubility parameter of the monomer composition containing a plurality of monomers is calculated for each monomer contained in the monomer composition by calculating the product of the solubility parameter and the mass ratio in the composition, It can be calculated by summing the obtained products.
- the Fedors method see Polymer Engineering and c Science, 1974, vol. 14, p. 147-154.
- a core vinyl monomer and / or a silane monomer are conventionally known aqueous suspension polymerization, dispersion polymerization, emulsification.
- Method of polymerizing by polymerization (ii) A method of polymerizing (radical polymerization) the vinyl group-containing polysiloxane and the core vinyl monomer after obtaining the vinyl group-containing polysiloxane using the core silane monomer (Iii) a so-called seed polymerization method in which the seed particles absorb the vinyl monomer for the core and polymerize (preferably radical polymerization);
- a catalyst necessary for the polymerization reaction such as a polymerization initiator is mixed with the core monomer composition.
- the polymerization initiator is preferably uniformly dispersed or dissolved in the composition.
- a surfactant may be used, and the amount used is 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the monomer composition for core. It is preferable that it exists in the range.
- the surfactant used in the step (a) can be removed by washing the obtained core particles with an organic solvent such as ion-exchanged water or methanol.
- the production methods (ii) and (iii) are preferable, and from the viewpoint of being industrially advantageous, the production method (i) is preferable.
- the method for forming the core particles can be appropriately selected depending on the intended application.
- the said vinyl monomer for cores can be especially used without a restriction
- a silane monomer for cores a silane crosslinkable monomer is preferable, the silane crosslinkable monomer having two or more vinyl groups (first form), a di- or trialkoxy having a vinyl group.
- a silane crosslinkable monomer having a vinyl group such as silane (third form) is more preferred.
- an aqueous suspension polymerization is taken as an example.
- a composition obtained by mixing a core monomer composition with a (radical) polymerization initiator is suspended in an aqueous medium (for example, water), The core is obtained by heating with stirring (usually 50 to 100 ° C.).
- a core particle into which a polysiloxane skeleton is introduced can be obtained by using a silane crosslinkable monomer capable of forming at least the third form as a core silane monomer. .
- grains with a non-crosslinked or low crosslinking degree are used as seed particles.
- the polysiloxane particles as the seed particles include a composition containing a silane crosslinkable monomer capable of forming the third form (crosslinking between vinyl polymer and polysiloxane).
- (Co) hydrolytic condensation is preferable, and vinyl group-containing polysiloxane particles are particularly preferable.
- Such a vinyl group-containing polysiloxane particle as the core particle has, for example, a silane crosslinkable monomer (preferably having a vinyl group) capable of forming the third form (crosslinking between vinyl polymer and polysiloxane). It can be produced by (co) hydrolytic condensation of a silane monomer (which may be a mixture) containing a di- or trialkoxysilane.
- the core monomer composition means a combination of seed particles and a core vinyl monomer to be absorbed by the seed particles.
- the solubility parameter of the core monomer composition is calculated by adding the product of the seed particle mass ratio and the solubility parameter and the product of the mass ratio and solubility parameter of each of the core vinyl monomers. can do.
- the solubility parameter of the seed particles is the same as the solubility parameter of the monomer composition forming the seed particles.
- an emulsion of the core vinyl monomer is mixed with stirring while the seed particles are dispersed in a solvent, whereby the core vinyl single unit is mixed with the seed particles.
- the core can be produced by allowing the polymer to be absorbed and further heating to advance the polymerization reaction.
- the solvent for dispersing the seed particles water or an organic solvent containing water as a main component is preferable.
- the emulsion containing the core vinyl monomer an emulsion obtained by emulsifying a mixture of the core vinyl monomer and the polymerization initiator in water is preferably used.
- the heating temperature is preferably in the range of 50 to 100 ° C.
- the surface of the core particles is coated with a silane monomer composition containing a silane monomer as a polymerization component to form a shell, and the present invention.
- the resin particles 1 can be obtained. Thereby, a convex part can be formed appropriately and the resin particle of this invention can be obtained efficiently.
- the predetermined convex portion can be formed even if the melting point of the resin forming the convex portion is 200 ° C. or higher.
- silane monomer used in the silane monomer composition in the step (b) (hereinafter referred to as “shell silane monomer”), a silane crosslinkable monomer can be preferably used.
- the melting point of the convex portion becomes 200 ° C. or higher, and in the obtained shell, the vinyl polymer and the polysiloxane skeleton are bonded via the silicon atoms constituting the polysiloxane, so that not only the elastic characteristics and the restoring force are obtained.
- the refractive index is improved, the light diffusing ability and the like are also improved.
- the silane monomer for the shell is more preferably a silane crosslinkable monomer capable of forming the third form (crosslinking between vinyl polymer and polysiloxane), more preferably a silane crosslinkable monomer having a vinyl group.
- a dimer or trialkoxysilane having a vinyl group is particularly preferred.
- the silane monomer for shell one kind may be used alone, or two or more kinds may be used in combination.
- a silane crosslinkable monomer capable of forming the third form (crosslinking between vinyl polymer and polysiloxane) is used as the silane monomer for the shell. preferable.
- the solubility parameter of the silane monomer composition for shell is preferably 6 (cal / cm 3 ) 1/2 or more, and preferably 10 (cal / cm 3 ) 1/2 or less.
- the solubility parameter of the silane monomer composition for shell is more preferably 6.5 (cal / cm 3 ) 1/2 or more, and further preferably 7 (cal / cm 3 ) 1/2 or more.
- the solubility parameter of the silane monomer composition for shell is more preferably 9.5 (cal / cm 3 ) 1/2 or less, and further preferably 9 (cal / cm 3 ) 1/2 or less. The larger the solubility parameter, the higher the hydrophilicity of the shell silane monomer composition, and the lower the solubility parameter, the higher the hydrophobicity of the shell silane monomer composition.
- the shell silane monomer is different from the core monomer composition in terms of hydrophilicity / hydrophobicity in order to easily form a convex portion.
- the absolute value of the difference ⁇ SP in the solubility parameter between the core monomer composition and the shell silane monomer composition is 0.35 (cal / cm 3 ) 1/2 or more. preferable.
- the absolute value of the difference in solubility parameter is larger, the difference in hydrophilicity / hydrophobicity is larger, so that the convex portion is more easily formed.
- the absolute value of the difference in solubility parameter between the core monomer composition and the shell silane monomer composition is more preferably 0.4 (cal / cm 3 ) 1/2 or more, Preferably, it is 0.45 (cal / cm 3 ) 1/2 or more. Further, if the difference in solubility parameter becomes too large, the core and the shell may be separated due to the difference in hydrophilicity / hydrophobicity. Therefore, the absolute value of the difference in solubility parameter between the core monomer composition and the shell silane monomer composition is preferably, for example, 10 (cal / cm 3 ) 1/2 or less, more preferably 5 (Cal / cm 3 ) 1/2 or less, more preferably 3 (cal / cm 3 ) 1/2 or less.
- the mass ratio of the core monomer composition to the shell silane monomer composition is 0.00. It is preferably 025 or more and 1 or less.
- the mass ratio (the silane monomer composition for the shell / the monomer composition for the core) can be selected according to the use of the resin particles and the size, number, etc.
- the solubility parameter of the shell silane monomer is calculated as the sum of the product of the solubility parameter of each monomer and its mass ratio. it can.
- a method of forming the shell by coating the surface of the core particle with the silane monomer composition for shell a method of (co) hydrolytic condensation of the silane monomer composition for shell on the surface of the core particle; preferable.
- resin particles in which a shell is formed on the surface of the core particle by adding and mixing the silane monomer composition for the shell while stirring a liquid in which the core particle is dispersed in a solvent containing water and a hydrolysis catalyst 1 is obtained.
- the solvent for dispersing the core particles water or an organic solvent excellent in water solubility is preferable, and water, methanol, ethanol or 2-propanol is more preferable.
- the solvent for dispersing the core particles one kind may be used alone, or two or more kinds may be mixed and used.
- the reaction temperature is preferably in the range of 0 to 100 ° C, more preferably 10 to 50 ° C.
- the resin particle 1 in which the shell was formed on the surface of the core particle can also be obtained by adding and mixing the silane monomer composition for shell to the reaction solution in which the core particle is dispersed after the polymerization of the core particle. .
- step (c) described later when a silane crosslinkable monomer having a vinyl group is used as the silane monomer for the shell, polymerization of the vinyl group is performed after the hydrolysis condensation reaction. It is preferable to carry out the reaction. Specifically, the reaction liquid after the hydrolysis condensation reaction may be heated (preferably 50 to 100 ° C.) in the presence of a polymerization initiator. As a result, resin particles 1 having a polysiloxane component (polysiloxane skeleton) and a vinyl polymer (skeleton) and a shell layer having a vinyl polymer-polysiloxane cross-link (third form) are obtained. .
- the resin particle 1 obtained in step (b) is made to absorb a vinyl monomer composition for a shell containing a vinyl monomer as a polymerization component. After polymerization, the resin particles 2 of the present invention can be obtained.
- the vinyl monomer used in the shell vinyl monomer composition (hereinafter referred to as “shell vinyl monomer”) can be selected from the vinyl monomers exemplified above.
- a vinyl monomer for shell a monomer having two or more vinyl groups (1), a monomer having one vinyl group and a binding functional group other than vinyl groups (2 ) And a monomer (3) having one vinyl group.
- the vinyl monomer for shell one kind may be used alone, or two or more kinds may be used, but two or more kinds are preferably used from the viewpoint of adjusting mechanical properties, optical properties and the like.
- the monomer (1) having two or more vinyl groups di (meth) acrylates and aromatic hydrocarbon crosslinking agents are preferable.
- the monomer (2) having one vinyl group and a binding functional group other than the vinyl group hydroxy group-containing (meth) acrylates are preferable.
- a monomer (3) which has one vinyl group alkyl (meth) acrylates and a styrene monofunctional monomer are preferable.
- the vinyl monomer composition for shell may contain a monomer other than the vinyl monomer for shell, but it is preferable that the vinyl monomer for shell is a main component.
- the mass ratio of the vinyl monomer for shell is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 98% by mass or more. Especially preferably, it is 100 mass%.
- the proportion of the vinyl crosslinkable monomer is preferably 10% by mass or more, and more preferably 15% by mass. As the proportion of the vinyl crosslinkable monomer increases, the contact angle of the convex portion tends to increase.
- the upper limit of the ratio of the vinyl crosslinkable monomer is 100% by mass.
- the solubility parameter of the vinyl monomer composition for shell is preferably 8 (cal / cm 3 ) 1/2 or more, and preferably 11 (cal / cm 3 ) 1/2 or less.
- the solubility parameter of the vinyl monomer composition for shell is more preferably 8.5 (cal / cm 3 ) 1/2 or more, further preferably 8.9 (cal / cm 3 ) 1/2 or more, particularly preferably 9.1 (cal / cm 3 ) 1/2 or more.
- the solubility parameter of the vinyl monomer composition for shells is more preferably 10.5 (cal / cm 3 ) 1/2 or less, and further preferably 10 (cal / cm 3 ) 1/2 or less. The higher the solubility parameter, the higher the hydrophilicity of the vinyl monomer composition for shells, and the lower the solubility parameter, the higher the hydrophobicity of the vinyl monomer composition for shells.
- the absolute value of the difference between the solubility parameter of the shell vinyl monomer composition and the solubility parameter of the core monomer composition is preferably 0.1 (cal / cm 3 ) 1/2 or more. As the absolute value of the solubility parameter difference increases, the contact angle of the convex portion tends to increase.
- the absolute value of the difference in solubility parameter is preferably 1.0 (cal / cm 3 ) 1/2 or less, and more preferably 0.9 (cal / cm 3 ) 1/2 or less.
- the mass ratio of the shell vinyl monomer composition to the shell silane monomer is 0.05. As mentioned above, it is preferable that it is 50 or less.
- the mass ratio (the vinyl monomer composition for shell / the silane monomer for shell) can be selected according to the use of the resin particles and the size, number, etc. of the desired convex portions, more preferably 0. 0.1 or more, more preferably 0.15 or more, more preferably 40 or less, and still more preferably 35 or less.
- the polymerization method after absorbing the shell vinyl monomer is preferably radical polymerization.
- the vinyl monomer for shell is absorbed by mixing the emulsion of the vinyl monomer composition for shell while stirring with the resin particles 1 dispersed in a solvent. Then, the resin particles 2 can be produced by heating to advance the polymerization reaction.
- a preferable solvent in which the resin particles 1 are dispersed includes a solvent in which the core particles in the step (b) are dispersed.
- the emulsion containing the shell vinyl monomer composition an emulsion obtained by emulsifying a mixture of the shell vinyl monomer composition and the polymerization initiator in water is preferably used.
- a surfactant preferably an anionic surfactant
- the amount used is, for example, 1 to 10 parts by mass with respect to 100 parts by mass of the vinyl monomer for core. It is preferably 1 to 5 parts by mass.
- a dispersion aid may be used in combination. The amount of the dispersion aid used is preferably, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the surfactant.
- the heating temperature is preferably in the range of 50 to 100 ° C.
- the obtained fine particles may be classified as necessary, dried, or fired.
- the drying temperature is not particularly limited, but is usually preferably in the range of 50 ° C to 350 ° C.
- the resin particles of the present invention can be produced by the above-described production method. 4).
- Conductive fine particles The conductive fine particles of the present invention have the resin particles and a conductive metal layer that covers the convex portions of the resin particles along the convex shape.
- the resin particles are resin particles composed of a peripheral portion having a plurality of convex portions on the surface and a spherical portion surrounded by the peripheral portion, and a cross section of the resin particles is observed with a transmission electron microscope In this case, the center of curvature of the boundary line between the peripheral edge portion and the spherical portion is present in the spherical portion. Thereby, since the detachment
- resin particles used for the conductive fine particles of the present invention resin particles having different convex portions (height, bottom diameter, constituent components, number density, etc.) may be mixed and used as substrate particles.
- Examples of the metal constituting the conductive metal layer include gold, silver, copper, platinum, iron, lead, aluminum, chromium, palladium, nickel, rhodium, ruthenium, antimony, bismuth, germanium, tin, cobalt, indium and nickel.
- -Metals such as phosphorus and nickel-boron, metal compounds, and alloys thereof.
- gold, nickel, palladium, silver, copper, and tin are preferable because they become conductive fine particles having excellent conductivity.
- nickel, nickel alloys Ni—Au, Ni—Pd, Ni—Pd—Au, Ni—Ag, Ni—P, Ni—B, Ni—Zn, Ni—Sn, Ni—W, Ni—Co, Ni—W, Ni—Ti
- copper, copper alloy Cu and Fe, Co, Ni, Zn, Sn, In, Ga, Tl, Zr, W, Mo, Rh, Ru, Ir, Ag, Alloy with at least one metal element selected from the group consisting of Au, Bi, Al, Mn, Mg, P, B, preferably an alloy with Ag, Ni, Sn, Zn
- Silver, silver alloy Ag And Fe, Co, Ni, Zn, Sn, In, Ga, Tl, Zr, W, Mo, Rh, Ru, Ir, Au, Bi, Al, Mn, Mg, P, B Alloy with one metal element, preferably Ag-Ni, Ag-Sn, Ag-Z ); Tin, tin alloy (eg, Sn
- the conductive metal layer may be a single layer or multiple layers. In the case of multiple layers, for example, a combination of nickel-gold, nickel-palladium, nickel-palladium-gold, nickel-silver, etc. Are preferred.
- the thickness of the conductive metal layer is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, further preferably 0.05 ⁇ m or more, preferably 0.3 ⁇ m or less, more preferably 0.25 ⁇ m or less, More preferably, it is 0.2 micrometer or less, More preferably, it is 0.15 micrometer or less.
- the resin particles used as the substrate have convex portions
- the convex portions of the resin particles are formed on the surface even after the conductive fine particles are formed. Convex portions corresponding to are formed, and the connection stability is improved.
- the thickness of the conductive metal layer can be measured, for example, by a method described later in Examples.
- the conductive metal layer only needs to cover at least a part of the surface of the resin particles, but the surface of the conductive metal layer has no substantial cracks or conductive metal layer. Is preferably absent.
- substantially cracked or a surface on which the conductive metal layer is not formed means that the surface of any 10,000 conductive fine particles is observed using a scanning electron microscope (magnification 1000 times). Furthermore, it means that the crack of the conductive metal layer and the exposure of the resin particle surface are not substantially visually observed.
- the volume average particle diameter of the conductive fine particles of the present invention is preferably 1 ⁇ m or more, more preferably 1.1 ⁇ m or more, further preferably 1.6 ⁇ m or more, still more preferably 2.1 ⁇ m or more, and preferably 51 ⁇ m or less, More preferably, it is 50 micrometers or less, More preferably, it is 41 micrometers or less, More preferably, it is 36 micrometers or less, More preferably, it is 31 micrometers or less. If the volume average particle diameter is in this range, it can be suitably used for electrical connection of electrodes and wirings that are miniaturized and narrowed.
- the coefficient of variation (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 even more preferably 4.5%. Hereinafter, it is particularly preferably 4.0% or less.
- the volume average particle size of the conductive fine particles was determined using a flow type particle image analyzer (“FPIA (registered trademark) -3000” manufactured by Sysmex Corporation), and the average particle size based on the number of 3000 particles. Is preferably adopted.
- the conductive fine particles of the present invention may have an insulating resin layer on at least a part of the surface. That is, the aspect which provided the insulating resin layer further on the surface of the said electroconductive metal layer may be sufficient.
- the insulating resin layer is further laminated on the conductive metal layer on the surface in this way, it is possible to prevent the lateral conduction that is likely to occur when a high-density circuit is formed or when a terminal is connected.
- the insulating resin layer is not particularly limited as long as the insulating property between the particles of the conductive fine particles can be secured, and the insulating resin layer can be easily collapsed or peeled off by a certain pressure and / or heating.
- polyolefins such as polyethylene; (meth) acrylate polymers and copolymers such as polymethyl (meth) acrylate; thermoplastic resins such as polystyrene; and cross-linked products thereof; epoxy resins, phenol resins, amino resins (melamine resins, etc.) And the like; and water-soluble resins such as polyvinyl alcohol and mixtures thereof.
- the insulating resin layer is too hard compared with the base particle (resin particle), the base particle (resin particle) itself may be destroyed before the insulating resin layer is destroyed. Therefore, it is preferable to use an uncrosslinked or relatively low degree of crosslinking resin for the insulating resin layer.
- the insulating resin layer may be a single layer or a plurality of layers. For example, 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. Further, it may be a layer formed by chemically modifying the surface of the conductive metal layer, or a combination thereof.
- the thickness of the insulating resin layer is preferably 0.01 ⁇ m or more and 1 ⁇ m or less, more preferably 0.02 ⁇ m or more and 0.5 ⁇ m or less, and further preferably 0.03 ⁇ m or more and 0.4 ⁇ m or less. If the thickness of the insulating resin layer is within the above range, the electrical insulation between the particles is good while maintaining the conduction characteristics by the conductive fine particles.
- the formation method of the conductive metal layer and the formation method of the insulating resin layer are not particularly limited.
- the conductive metal layer is plated on the substrate surface by an electroless plating method, an electrolytic plating method, or the like; Or a method of forming a conductive metal layer by a physical vapor deposition method such as vacuum vapor deposition, ion plating, or ion sputtering;
- the electroless plating method is particularly preferable in that a conductive metal layer can be easily formed without requiring a large-scale apparatus.
- An anisotropic conductive material of the present invention includes the conductive fine particles of the present invention and a binder resin, and the conductive fine particles are dispersed in the 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). Suitable applications of the anisotropic conductive material include touch panel input, LED use, and the like, and particularly suitable for touch panel mounting.
- the binder resin is an insulating resin, for example, a thermoplastic resin such as an acrylic resin, an ethylene-vinyl acetate resin, a styrene-butadiene block copolymer; a curing agent such as a monomer or oligomer having a glycidyl group and isocyanate. Curable resin composition cured by reaction with curable resin; curable resin composition cured by light or heat; and the like.
- the anisotropic conductive material of the present invention can be obtained by dispersing the conductive fine particles of the present invention in the binder resin to obtain a desired form.
- the binder resin and the conductive fine particles are separately provided. You may connect by making electroconductive fine particles exist with a binder resin between the base material to be used and connecting between electrode terminals.
- the content of the conductive fine particles may be appropriately determined according to the use.
- the content is preferably 1% by volume or more, more preferably 2% in the total amount of the anisotropic conductive material.
- Volume% or more More preferably, it is 5 volume% or more, 50 volume% or less is preferable, More preferably, it is 30 volume% or less, More preferably, it is 20 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 film thickness in the anisotropic conductive material of the present invention about the film thickness in the anisotropic conductive material of the present invention, the coating thickness of the paste or adhesive, the printed film thickness, etc., the particle diameter of the conductive fine particles of the present invention to be used and the specifications of the electrode to be connected.
- the particle size ( ⁇ m) of 30000 particles was measured by “type”), and the volume average particle size was determined.
- the standard deviation of the particle size on the volume basis was obtained together with the volume average particle size, and the coefficient of variation (CV value) of the particle size was calculated according to the following formula.
- Variation coefficient of particle diameter (%) 100 ⁇ (standard deviation of particle diameter / volume average particle diameter)
- ⁇ Average height of protrusions, average base diameter> In an SEM image obtained by photographing a resin particle at a magnification of 10,000 times or more using a scanning electron microscope (SEM), the boundary of the convex portion and the boundary of the spherical portion that exist at the peripheral portion of the resin particle intersect 2 Connect the points with line segments, make the distance between the line segment and the most convex part of the convex part the height, and the length of the line segment (distance between two points where the boundary of the convex part and the boundary of the spherical part intersect) Measured as bottom diameter. The height and base diameter of 50 convex portions per one type of resin particles were measured and averaged to obtain the average height and average base diameter of the convex portions of the resin particles.
- ⁇ Number density of protrusions> Using a scanning electron micrograph taken at a magnification of 10,000 times or more, the diameter of the spherical portion or the diameter including the spherical portion and the peripheral layer was calculated using a caliper diameter calculation tool attached to the apparatus.
- the number of convex parts per resin particle is the surface area of the spherical part (4 ⁇ ⁇ ⁇ the square of the radius of the spherical part) or the surface area of the peripheral layer (4 ⁇ ⁇ ⁇ (the sum of the radius of the spherical part and the thickness of the peripheral layer). Divided by the square of).
- SEM scanning electron microscope
- the drop-off property of the protrusions was judged according to the following criteria from the average value of the number of protrusions per particle before and after the treatment.
- the value of (average value of the number of protrusions per particle after treatment) / (average value of the number of protrusions per particle before treatment) exceeds 0.9, “ ⁇ ”, 0.9 or less was evaluated as “ ⁇ ”.
- ⁇ Measuring method of melting point> The glass plate on which the particles were dispersed was placed in a heating furnace heated to a predetermined temperature, and heat-treated for 60 minutes. The particles before and after the heat treatment were observed with an SEM, and the temperature at which the shape of the contact point between the particles and the glass plate was changed was defined as the melting point of the peripheral portion.
- an anisotropic conductive material (anisotropic conductive paste) was prepared by the following method, and the presence or absence of indentation and the initial resistance value were evaluated by the following method. .
- the initial resistance value and the evaluation result of the indentation are shown in Table 5. That is, using a rotating and rotating stirrer, 100 parts of an epoxy resin (“Stractbond (registered trademark) XN-5A” manufactured by Mitsui Chemicals) as a binder resin was added to 2.0 parts of conductive fine particles and stirred for 10 minutes. And dispersed to obtain a conductive paste.
- an epoxy resin (“Stractbond (registered trademark) XN-5A” manufactured by Mitsui Chemicals)
- the obtained anisotropic conductive paste is sandwiched between a glass substrate on which ITO electrodes are wired at a pitch of 100 ⁇ m and a glass substrate on which an aluminum pattern is formed at a pitch of 100 ⁇ m, and is thermocompression bonded under pressure bonding conditions of 2 MPa and 150 ° C.
- the connection structure was obtained by curing the binder resin.
- Table 1 shows the abbreviations and solubility parameters of monomers used for production of resin particles.
- nBMA 850 parts, MMA 850 parts, HEMA 150 parts, 16HXA 150 parts as core monomer components (core vinyl monomer), 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure) A solution in which 42 parts of “V-65” (manufactured by Yakuhin Kogyo Co., Ltd.) were dissolved was added and emulsified and dispersed to prepare an emulsion containing the core monomer component (core vinyl monomer).
- the obtained emulsion was added with an emulsion of polysiloxane particles and stirred for 1 hour. Further, 840 parts of a 10% aqueous solution of polyvinyl alcohol and 2000 parts of ion-exchanged water were added, and the reaction solution was heated to 65 ° C. under a nitrogen atmosphere. The temperature was raised and held for 2 hours to perform radical polymerization of the monomer component. The emulsion after radical polymerization was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol, and then vacuum-dried at 40 ° C. for 12 hours to obtain core particles 1. The particle diameter, coefficient of variation (CV value), and degree of crosslinking of the core particle 1 were as shown in Table 2.
- a core particle 12 was obtained in the same manner as in Synthesis Example 10 (core particle 10) except that the type and amount of the monomer composition for core were changed as shown in Table 2. Furthermore, it classified using the mesh of 8 micrometers of openings, and 15 micrometers, and obtained the core particle 13.
- FIG. The particle diameter, coefficient of variation (CV value), and degree of crosslinking of the core particles 12 and 13 were as shown in Table 2.
- the particle size before classification was 12.84 ⁇ m, and the coefficient of variation (CV value) was 30.7%.
- Polysiloxane particles seed particles were prepared by appropriately changing the amounts of the silane monomer for the core, ion exchange water, methanol, and ammonia water, and the types and amounts of the vinyl monomer for the core are shown in Table 2.
- a core particle 14 was obtained in the same manner as in Synthesis Example 1 except that The core particles 14 were as shown in Table 2.
- emulsifier 0.4 part of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., “Hitenol (registered trademark) NF-08”) as an emulsifier is added with 15 parts of ion-exchanged water.
- 15 parts of CHMA as a core monomer component (core vinyl monomer) is added and emulsified and dispersed to prepare emulsion B containing the core monomer component (core vinyl monomer).
- the obtained emulsion A was added to an emulsion of polysiloxane particles, stirred for 1 hour, and then further polyoxyethylene styrenated phenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd., “Hitenol (registered trademark) 8.3 parts of 20% aqueous solution of NF-08 ”) was added, the reaction solution was heated to 65 ° C under a nitrogen atmosphere and held for 1 hour, then Emulsion B was added, and the reaction solution was further added under a nitrogen atmosphere. Was held at 65 ° C. for 2 hours to carry out 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 vacuum-dried at 120 ° C. for 2 hours to obtain core particles 15.
- the volume average particle diameter, the coefficient of variation (CV value), and the degree of crosslinking of the core particles 15 are as shown in Table 2.
- St30.8 as a monomer component for shell (vinyl monomer for shell) was added to a solution of 0.9 part of 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt dissolved in 100 parts of ion exchange water.
- DVB (“DVB960” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
- V-65 2,2′-azobis (2,4-dimethylvaleronitrile)
- a solution obtained by dissolving 0.04 part of Milling 4GW (manufactured by Nippon Kayaku Co., Ltd.) in 20 parts of ion-exchanged water is added, and the reaction solution is heated to 65 ° C. and held for 2 hours under a nitrogen atmosphere. Perform radical polymerization It was. 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 vacuum-dried at 40 ° C. for 12 hours to obtain resin particles (1).
- Resin particles (27) were obtained in the same manner as in Production Example 26 except that the core particles as shown in Table 4 were used as the core particles.
- DVB Denstrength (Nippon Steel) as a monomer component for shells (vinyl monomer for shells) was prepared by dissolving 0.2 parts of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfate ammonium salt with 100 parts of ion-exchanged water. 7.0 parts of “DVB960” manufactured by Sumikin Chemical Co., Ltd. and 2.1 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved.
- the mixture After adding the solution and emulsifying and dispersing the emulsified shell monomer component (shell vinyl monomer) to the core particle dispersion, the mixture is stirred for 1 hour and then dissolved in 21.0 parts of a 10% aqueous solution of polyvinyl alcohol. The solution was added, and the reaction solution was heated to 65 ° C. and held for 2 hours under a nitrogen atmosphere, and radical polymerization of the monomer component was performed. The emulsion after radical polymerization was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol, and then vacuum-dried at 80 ° C. for 4 hours to obtain resin particles (29).
- Mass ratio of the monomer composition for core and the silane monomer for shell in Production Examples 1 to 30 (silane monomer for shell / monomer composition for core), vinyl monomer for shell and shell Mass ratio of silane monomer (vinyl monomer for shell / silane monomer for shell), solubility parameter SP core of monomer composition for core , solubility parameter of silane monomer for shell and single amount for core Tables 3 and 4 show the difference (SP shell silane monomer-core monomer composition) ⁇ SP from the solubility parameter of the body composition.
- the resin particles obtained in Production Examples 1 to 7, 9 to 20, 22 to 25, 29, and 30 have a spherical portion and a plurality of convex portions formed on the surface thereof.
- the boundary line between the convex portion and the spherical portion had a structure that swelled toward the convex portion side, and the convex portion was difficult to be detached.
- the boundary line of the spherical portion is continuous without having an inflection point regardless of whether or not the convex portion exists, and the contact angle when the convex portion is assumed to be a droplet with respect to the spherical portion. was about 17 ° to 84 °.
- the resin particles obtained in Production Examples 1 to 7, 9 to 20, 22 to 25, 29, and 30 have a uniform size (height, base diameter) and distribution, as is apparent from FIGS. It is useful for additives for resins (anti-blocking agents, light diffusing agents, etc.), additives for decorative plates, fillers for cosmetics, and substrates for conductive fine particles.
- Examples 1 to 23, Comparative Examples 1 to 5 After the resin particles used as the base material are etched with sodium hydroxide, they are sensitized by bringing them into contact with a tin dichloride solution, and then activated by immersing them in a palladium dichloride solution. Palladium nuclei were formed by the taging-activation method). Next, 2 parts of resin particles with palladium nuclei formed were added to 400 parts of ion-exchanged water, and after ultrasonic dispersion treatment, the resulting resin particle suspension was heated in a 70 ° C. hot bath. By adding 600 parts of electroless plating solution (“Schumar S680” manufactured by Nippon Kanisen Co., Ltd.) separately heated to 70 ° C.
- electroless plating solution (“Schumar S680” manufactured by Nippon Kanisen Co., Ltd.) separately heated to 70 ° C.
- the base particles (resin particles) had a plurality of convex portions, and were excellent in conductivity when an anisotropic conductive material was used. Moreover, it was in the tendency for it to be excellent in electroconductivity, so that the contact angle of a convex part became large in the range of 90 degrees or less.
- Comparative Examples 1 and 2 using base particles (resin particles) having no convex part and Comparative Examples 3 to 3 in which the center of curvature of the boundary line between the peripheral part and the spherical part does not exist in the spherical part. No. 5 was inferior in conductivity because the convex portion was easily detached when an anisotropic conductive material was used.
- the resin particles of the present invention have a uniform size of protrusions and density of protrusions, and the protrusions are not easily detached, additives for resins (anti-blocking agents, light diffusing agents, etc.), decorative boards Can be used in a wide range of applications such as additives for cosmetics, fillers for cosmetics, and substrates of conductive fine particles.
- the conductive fine particles of the present invention are composed of resin particles having a plurality of convex portions on the surface and a conductive metal layer covering the convex shape, the conductive portions are less likely to be detached. Fine particles can be obtained regardless of plating conditions. For this reason, it is extremely useful for anisotropic conductive materials such as anisotropic conductive films, anisotropic conductive pastes, anisotropic conductive adhesives, and anisotropic conductive inks.
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Abstract
Description
また本発明は、めっき条件によらず、突起の脱離が抑制され、十分な接続信頼性を確保しうる導電性微粒子を提供することを課題とする。
さらに本発明の導電性微粒子は、基材粒子として特定の凸部を有する樹脂粒子を用いているため、導電性微粒子表面の突起形状を制御でき、かつ突起の脱離が抑制されたものとなる。
本発明の樹脂粒子は、球状部とその表面に形成された複数の凸部を有する周縁部とから構成され、周縁部は、前記球状部の表面に形成されており、球状部は前記周縁部に囲まれている。そして周縁部は、前記複数の凸部を有する。さらに本発明の樹脂粒子の断面を走査透過電子顕微鏡で観察したときの前記周縁部と球状部の間の境界線の曲率中心は球状部に存在する。これにより、凸部が脱離しにくいものとなる。後述するように、樹脂粒子断面の透過型電子顕微鏡写真において、通常、周縁部は暗色部として表示され、球状部は明色部として表示される。
本発明において、凸部とは、高さ(μm)と底辺直径(μm)の積、すなわち、高さ×底辺直径(μm2)が、0.001(μm2)以上のものを意味する。高さと底辺直径の積は、より好ましくは0.005(μm2)以上、さらに好ましくは0.009(μm2)以上である。上限は特に限定されないが、通常50(μm2)以下である。
本発明の樹脂粒子における周縁部は、ビニル重合体及び/又はポリシロキサン成分で形成されているが、周縁部を構成するビニル重合体及び/又はポリシロキサン成分の融点が、それぞれ200℃以上であることが、周縁部の融点を250℃とし易く、室温(25℃)における凸部の硬度を向上することができる点から好ましい。周縁部を構成する成分(ビニル重合体及び/又はポリシロキサン成分)の融点は、より好ましくは220℃以上、さらに好ましくは240℃以上、一層好ましくは250℃以上である。融点の上限は特に限定されないが、例えば400℃である。
本発明の樹脂粒子は、ビニル重合体及び/又はポリシロキサン成分で形成されており、ビニル重合体とポリシロキサン成分とで形成されているものであることがより好ましい。本発明において、ビニル重合体は、ビニル重合体骨格を有する重合体を意味し、ビニル単量体(ビニル基含有単量体)を重合(好ましくはラジカル重合)することによって形成できる。またポリシロキサン成分(ポリシロキサン骨格ともいう)は、シロキサン結合(Si-O-Si)を有する成分を意味し、シラン単量体を重合することによって形成できる。ポリシロキサン成分としては、シラン架橋性単量体(好ましくは第三の形態のシラン架橋性単量体、より好ましくはビニル基を有するシラン単量体)を用いて形成されたポリシロキサン成分が好ましい。
ここで、前記球状部や周縁部の組成は、球状部、周縁部を形成する各単量体の種類と質量割合で表現し、同様に、ビニル重合体やポリシロキサン成分の組成は、ビニル重合体、ポリシロキサン成分を形成する各単量体の種類と質量割合で表現する。従って、「球状部と周縁部との組成が異なる」とは、球状部を形成する単量体と、周縁部を形成する単量体とで、その種類や質量割合とが異なることを意味し、例えば、球状部を構成するビニル重合体と、周縁部を構成するビニル重合体とが異なる組成である場合や、球状部を構成するポリシロキサン成分と、周縁部を構成するポリシロキサン成分とが異なる組成である場合等のように、球状部および周縁部をそれぞれ構成するビニル重合体及びポリシロキサン成分の少なくともいずれか一方の組成が異なる態様;球状部および周縁部中の、ビニル重合体及びポリシロキサン成分の少なくともいずれか一方の含有量(球状部又は周縁部中の質量割合)が異なる態様;球状部および周縁部に含まれるビニル重合体、ポリシロキサン成分以外の第3成分の組成あるいは含有量(球状部又は周縁部中の質量割合)が異なる態様;などが包含される。中でも、球状部および周縁部をそれぞれ構成するビニル重合体及びポリシロキサン成分の少なくともいずれか一方の組成が異なる態様;球状部および周縁部中のビニル重合体及びはポリシロキサン成分の少なくともいずれか一方の含有量(球状部又は周縁部中の質量割合)が異なる態様が好ましい。なお、前記ビニル重合体、ポリシロキサン成分の組成が異なる場合には、球状部と周縁部のいずれか一方が、ビニル重合体又はポリシロキサン成分を含有しない場合も包含する。
同様に、球状部に含まれるコア部と周縁部(凸部)が含まれるシェル部の組成が異なることが好ましい。たとえば、コア部を構成するビニル重合体またはポリシロキサン成分と、シェル部を構成するビニル重合体またはポリシロキサン成分の組成が異なる態様、コア部およびシェル部中のビニル重合体及びポリシロキサン成分の少なくともいずれか一方の含有量(質量割合)が異なる態様などが好ましく挙げられる。
これにより、凸部のサイズ(高さ、底辺直径)や、凸部の分散密度を調整できる。
また、球状部を形成する成分は、少なくともビニル重合体を含むことが好ましく、ビニル重合体とポリシロキサン成分を含むことがより好ましい。周縁部を形成する成分は、少なくともポリシロキサン成分を含むことが好ましく、ビニル重合体とポリシロキサン成分を含むことがより好ましい。
同様に、コア部を形成する成分は、少なくともビニル重合体を含むことが好ましく、ビニル重合体とポリシロキサン成分を含むことがより好ましい。シェル部を形成する成分は、少なくともポリシロキサン成分を含むことが好ましく、ビニル重合体とポリシロキサン成分を含むことがより好ましい。
前記ビニル架橋性単量体とは、ビニル基を有し架橋構造を形成し得るものであり、具体的には、1分子中に2個以上のビニル基を有する単量体(単量体(1))、又は1分子中に1個のビニル基とビニル基以外の結合性官能基(カルボキシ基、ヒドロキシ基等のプロトン性水素含有基、アルコキシ基等の末端官能基等)を有する単量体(単量体(2))が挙げられる。ただし、単量体(2)によって架橋構造を形成させるには、当該単量体(2)のビニル基以外の結合性官能基と反応(結合)可能な相手方単量体の存在が必要である。
第二の形態(ポリシロキサン間架橋)を形成し得るシラン架橋性単量体としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラブトキシシラン等の4官能性シラン単量体;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等の3官能性シラン単量体等が挙げられる。
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架橋性単量体としては、例えば、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-アクリロキシプロピルトリエトキシシラン、3-メタクリロキシエトキシプロピルトリメトキシシラン等の(メタ)アクリロイル基を有するジ又はトリアルコキシシラン;ビニルトリメトキシシラン、ビニルトリエトキシシラン、p-スチリルトリメトキシシラン等のビニル基(エテニル基)を有するジ又はトリアルコキシシラン;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;が挙げられる。これらのシラン架橋性単量体は単独で使用してもよいし、2種以上を併用してもよい。
本発明の樹脂粒子に、ポリシロキサン成分を導入する場合、ビニル単量体の使用量は、シラン単量体100質量部に対して1質量部以上が好ましく、より好ましくは5質量部以上、さらに好ましくは10質量部以上であり、5000質量部以下が好ましく、より好ましくは4000質量部以下、さらに好ましくは3000質量部以下である。
本発明の樹脂粒子は、
工程(a):ビニル単量体及び/又はシラン単量体を重合成分として含むコア用単量体組成物を重合して、コア粒子を形成する工程、
工程(b):前記コア粒子の表面に、シラン単量体を重合成分として含むシラン単量体組成物を被覆しシェルを形成して、樹脂粒子1を得る工程、
を含む製造方法により製造することができる。前記製造方法は、さらに、
工程(c):工程(b)で得られた樹脂粒子1に、ビニル単量体を重合成分として含むシェル用ビニル単量体組成物を吸収させた後、重合して、樹脂粒子2を得る工程
を含むことが好ましい。
工程(a)では、上記単量体を重合成分として含むコア用単量体組成物を重合することによって、本発明の樹脂粒子のコアを製造することができる。コア用単量体組成物に使用する単量体により、樹脂粒子の機械的性質、光学的性質を調整することができる。なお、「単量体組成物」は、単量体のみで構成される組成物を意味する。
ただし、コア用単量体組成物を重合するにあたっては、通常は、重合開始剤などの触媒成分を該組成物と共存させた状態で行う。
コア用ビニル単量体の割合がこの範囲にあると、特に、小粒径のコア粒子を得やすくなる。
なお、(i)~(iii)いずれの方法においても、コア用単量体組成物を重合するにあたっては、重合開始剤等の重合反応に必要な触媒をコア用単量体組成物と混合し、該組成物に重合開始剤を均一に分散または溶解させることが好ましい。また製造方法(i)~(iii)においては、界面活性剤を使用してもよく、その使用量は、コア用単量体組成物の合計100質量部に対して0.1~5質量部の範囲にあることが好ましい。工程(a)で使用する界面活性剤は、得られたコア粒子をイオン交換水、メタノール等の有機溶剤で洗浄することにより除去できる。
前記製造方法(ii)においては、コア用シラン単量体として、少なくとも前記第三の形態を形成し得るシラン架橋性単量体を用いることによって、ポリシロキサン骨格が導入されたコア粒子が得られる。
さらに、前記製造方法(iii)において、前記シード粒子としてのポリシロキサン粒子は、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ものであることが好ましく、特にビニル基含有ポリシロキサン粒子であることが好ましい。ポリシロキサン粒子がビニル基を有する場合、得られるコア粒子において、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、弾性特性や復元力のみならず、屈折率が向上することにより光拡散能等にも優れたものとなる。このようなコア粒子としてのビニル基含有ポリシロキサン粒子は、例えば、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架橋性単量体(好ましくは、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単量体(混合物でもよい))を(共)加水分解縮合することによって製造できる。
前記製造方法(iii)の具体例としては、例えば、シード粒子を溶媒に分散させた状態で攪拌しながら、コア用ビニル単量体の乳化液を混合することにより、シード粒子にコア用ビニル単量体を吸収させることができ、さらに加熱し重合反応を進めることによって、コアを製造することができる。シード粒子を分散させる溶媒としては、水または水を主成分とする有機溶媒が好ましい。またコア用ビニル単量体を含む乳化液としては、コア用ビニル単量体と重合開始剤との混合物を水に乳化させた乳化液を用いることが好ましい。加熱温度は、50~100℃の範囲が好ましい。
工程(b)では、前記コア粒子の表面に、シラン単量体を重合成分として含むシラン単量体組成物を被覆しシェルを形成して、本発明の樹脂粒子1を得ることができる。これにより、凸部を適切に形成でき、本発明の樹脂粒子を効率よく得ることができる。特に、上記方法によれば、凸部を形成する樹脂の融点が200℃以上であっても、所定の凸部を形成することができる。
また、後述する工程(c)を行わない場合、シェル用シラン単量体としては、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架橋性単量体を用いることが好ましい。
たとえば、コア粒子を水及び加水分解触媒を含む溶媒に分散させた液を攪拌しながら、シェル用シラン単量体組成物を添加混合することにより、コア粒子の表面にシェルが形成された樹脂粒子1が得られる。コア粒子を分散させる溶媒としては、水または水溶性に優れる有機溶媒が好ましく、水、メタノール、エタノールまたは2-プロパノールがより好ましい。前記コア粒子を分散させる溶媒は、1種を単独で使用してもよく、2種以上を混合して使用してもよい。反応温度は、0~100℃の範囲が好ましく、より好ましくは10~50℃である。また、コア粒子を重合した後のコア粒子が分散した反応溶液にシェル用シラン単量体組成物を添加混合することでも、コア粒子の表面にシェルが形成された樹脂粒子1を得ることができる。
工程(c)では、工程(b)で得られた樹脂粒子1に、ビニル単量体を重合成分として含むシェル用ビニル単量体組成物を吸収させた後、重合して、本発明の樹脂粒子2を得ることができる。
また、溶解度パラメータの差の絶対値は、1.0(cal/cm3)1/2以下であることが好ましく、0.9(cal/cm3)1/2以下であることがより好ましい。シェル用ビニル単量体組成物の溶解度パラメータとコア用単量体組成物の溶解度パラメータの差の絶対値がこの範囲にあると、凸部の形状の制御が容易である。
工程(c)の具体例としては、例えば、樹脂粒子1を溶媒に分散させた状態で攪拌しながらシェル用ビニル単量体組成物の乳化液を混合することによってシェル用ビニル単量体を吸収させた後、加熱し重合反応を進めることによって、樹脂粒子2を製造することができる。樹脂粒子1を分散させる好ましい溶媒としては、工程(b)におけるコア粒子を分散させた溶媒が挙げられる。シェル用ビニル単量体組成物を含む乳化液としては、シェル用ビニル単量体組成物と重合開始剤との混合物を水に乳化させた乳化液を用いることが好ましい。乳化させる際、界面活性剤(好ましくはアニオン性界面活性剤)を使用してもよく、その使用量は、コア用ビニル単量体100質量部に対して、例えば、1~10質量部であることが好ましく、1~5質量部であることがより好ましい。また、分散助剤を併用してもよい。分散助剤の使用量は、界面活性剤100質量部に対して、例えば0.1~10質量部であることが好ましい。上記加熱温度は、50~100℃の範囲が好ましい。
上述した製法により、本発明の樹脂粒子を製造することができる。
4.導電性微粒子
本発明の導電性微粒子は、上記樹脂粒子と、該樹脂粒子の表面凸部をこの凸部形状に沿って被覆する導電性金属層とを有するものである。前記樹脂粒子は、前記表面の複数の凸部を有する周縁部と、この周縁部に囲まれる球状部とから構成される樹脂粒子であり、かつ、前記樹脂粒子の断面を透過型電子顕微鏡で観察したときの前記周縁部と球状部の間の境界線の曲率中心が球状部に存在するものである。これにより、凸部の脱離が抑制されたものとなるため、導電性微粒子の接続信頼性が良好となる。
粒子径の変動係数(%)=100×(粒子径の標準偏差/体積平均粒子径)
なお、導電性微粒子の体積平均粒子径としては、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」)を用いて求めた、3000個の粒子の個数基準の平均粒子径を採用することが好ましい。
前記絶縁性樹脂層としては、導電性微粒子の粒子間における絶縁性が確保でき、一定の圧力及び/又は加熱により容易にその絶縁性樹脂層が崩壊あるいは剥離するものであれば特に限定されず、例えば、ポリエチレンなどのポリオレフィン類;ポリメチル(メタ)アクリレートなどの(メタ)アクリレート重合体および共重合体;ポリスチレン;等の熱可塑性樹脂やその架橋物;エポキシ樹脂、フェノール樹脂、アミノ樹脂(メラミン樹脂等)等の熱硬化性樹脂;ポリビニルアルコール等の水溶性樹脂およびこれらの混合物;等が挙げられる。但し、基材粒子(樹脂粒子)に比べて絶縁性樹脂層が硬過ぎる場合には、絶縁性樹脂層の破壊よりも先に基材粒子(樹脂粒子)自体が破壊してしまうおそれがある。したがって、絶縁性樹脂層には、未架橋または比較的架橋度の低い樹脂を用いることが好ましい。
本発明の異方性導電材料は、上記本発明の導電性微粒子とバインダー樹脂とを含み、導電性微粒子がバインダー樹脂に分散している。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、異方性導電インクなど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板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(導通スペーサーおよびその組成物)も含まれる。異方性導電材料の好適な用途としてはタッチパネルの入力用、LED用などが挙げられ、特にタッチパネルの実装用に好適に用いられる。
なお、本発明の異方性導電材料は、前記バインダー樹脂中に本発明の導電性微粒子を分散させ、所望の形態とすることで得られるが、例えば、バインダー樹脂と導電性微粒子とを別々に使用し、接続しようとする基材間や電極端子間に導電性微粒子をバインダー樹脂とともに存在させることによって接続してもかまわない。
各種物性の測定は以下の方法で行った。
<樹脂粒子の体積平均粒子径・変動係数(CV値)>
樹脂粒子及びコアの場合には、樹脂粒子又はコア0.1部に、乳化剤であるポリオキシエチレンアルキルエーテル硫酸エステルアンモニウム塩(第一工業製薬株式会社製「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、シード粒子の場合には、加水分解、縮合反応で得られた分散液をポリオキシエチレンアルキルエーテル硫酸エステルアンモニウム塩(第一工業製薬株式会社製「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て、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(μm)を測定し、体積平均粒子径を求めた。また樹脂粒子及びコアについては、体積平均粒子径とともに体積基準での粒子径の標準偏差をも求め、下記式に従って粒子径の変動係数(CV値)を算出した。
粒子径の変動係数(%)=100×(粒子径の標準偏差/体積平均粒子径)
樹脂粒子の断面を倍率10,000倍~30,000倍、加速電圧20kVの条件で、走査透過電子顕微鏡により撮影した。
走査型電子顕微鏡(SEM)を用い、倍率1万倍以上で樹脂粒子を撮影して得られたSEM画像において、樹脂粒子の周縁部に存在する凸部の境界と球状部の境界とが交わる2点を線分で結び、当該線分と凸部の最凸部との距離を高さとし、当該線分の長さ(凸部の境界と球状部の境界とが交わる2点間の距離)を底辺直径として測定した。1種類の樹脂粒子につき凸部50個の高さ及び底辺直径を測定し、平均して、樹脂粒子の凸部の平均高さ及び平均底辺直径とした。
走査型電子顕微鏡(SEM)を用い、倍率3000倍以上で樹脂粒子を撮影して、樹脂粒子上の凸部の個数を測定した。1種類の樹脂粒子につき5個の樹脂粒子の凸部の個数を測定し、平均し2倍して、樹脂粒子1個当たりの凸部の個数とした。
倍率1万倍以上で撮影した走査型電子顕微鏡写真を用い、装置付属のノギス径算出ツールを使用し、球状部の直径、又は球状部と周縁層を含めた直径を算出した。樹脂粒子1個当たりの凸部の個数を球状部の表面積(4×π×球状部の半径の二乗)又は周縁層の表面積(4×π×(球状部の半径と周縁層の厚みの合計)の二乗)で除して算出した。
樹脂粒子5個について、1個当たりの凸部の個数を算出してその標準偏差を算出し、下記式に従って、粒子間の凸部ばらつき指数とした。
粒子間の突起ばらつき指数=(粒子5個あたりの凸部の個数の標準偏差)/(樹脂粒子1個当たりの凸部の平均個数)
粒子を正投影面で見たときに、粒子中心にて互いに直交する線を2本引き、粒子を4区画に分割した。それぞれの区画について凸部の個数を測定し、1つの粒子における突起個数の標準偏差を算出した。1種類の樹脂粒子につき、5個の樹脂粒子の凸部の個数を測定し、標準偏差の平均値を算出し、下記式に従って、単一粒子上での突起ばらつき指数を算出した。
単一粒子上での突起ばらつき指数=(樹脂粒子1個当たりの凸部の標準偏差)/(樹脂粒子1個当たりの凸部の平均個数)
走査透過電子顕微鏡を用い、倍率1万倍以上で樹脂粒子の断面を撮影して、凸部の境界線と球状部の境界線とがなす角を接触角とした。さらに、1種類の樹脂粒子の凸部10個以上について接触角を測定し、平均して、樹脂粒子の凸部を球状部に対する液滴と仮定したときの接触角とした。
樹脂粒子1部にトルエン25部を加え、さらに直径1mmのジルコニアビーズを250部加えて、ステンレス製の2枚攪拌羽根を用い200rpmで10分間分散を行った。分散処理後、目開き500μmの金属製ふるいを通過させジルコニアビーズを除去し、メンブレンフィルター(3.0μm;アドバンテック社製)でろ過を行うことにより樹脂粒子を取り出し、乾燥させた。
得られた粒子を、走査型電子顕微鏡(SEM)を用い観察し、5個の粒子について突起数を算出した。突起の脱落性は、処理前後の粒子の1個あたりの突起数の平均値より以下の基準で判断した。
(処理後の粒子1個当たりの突起数の平均値)/(処理前の粒子1個当たりの突起数の平均値)の値が、0.9を超える場合を「○」、0.9以下を「×」と評価した。
粒子を散布したガラス板を所定温度に加熱した加熱炉に入れ、60分間加熱処理をした。加熱処理前後の粒子をSEMで観察し、粒子とガラス板との接点の形状が変化した温度を周縁部の融点とした。
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(樹脂粒子)3000個の個数平均粒子径X(μm)および導電性微粒子3000個の個数平均粒子径Y(μm)を測定した。なお、測定は、粒子0.25部に、乳化剤であるポリオキシエチレンオレイルエーテル(花王株式会社製「エマルゲン(登録商標)430」)の1.4%水溶液17.5部を加え、超音波で10分間分散させた後に行った。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
実施例および比較例で得られた導電性微粒子を用い、下記の方法で異方性導電材料(異方性導電ペースト)を作製し、圧痕形成の有無および初期抵抗値を下記の方法で評価した。その初期抵抗値および圧痕の評価結果は表5に示す。
すなわち、自転公転式攪拌機を用いて、導電性微粒子2.0部に、バインダー樹脂としてエポキシ樹脂(三井化学社製「ストラクトボンド(登録商標)XN-5A」)100部を添加して10分間攪拌して分散させ、導電性ペーストを得た。
得られた異方性導電ペーストを、100μmピッチにITO電極が配線されたガラス基板と100μmピッチにアルミパターンを形成したガラス基板との間に挟みこみ、2MPa、150℃の圧着条件で熱圧着するとともに、バインダー樹脂を硬化させることによって接続構造体を得た。
樹脂粒子の作製に用いたモノマーの略称、溶解度パラメータを表1に示す。
(合成例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部と、25%アンモニア水3部、メタノール600部を入れ、攪拌下、滴下口からコア用単量体成分(コア用シラン単量体)としてMPTMS(信越化学工業社製、「KBM503」)100部を添加して、MPTMS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シード粒子としての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。反応開始から2時間後、得られたポリシロキサン粒子の乳濁液をサンプリングし、粒子径を測定したところ、体積平均粒子径は6.06μmであった。
コア用シラン単量体、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て表2に示す通りの体積基準の平均粒子径のポリシロキサン粒子(シード粒子)を作製し、コア用ビニル単量体の種類と使用量を表2に示す通りに変更したこと以外は合成例1と同様にして、コア粒子2~9を得た。コア粒子2~9の粒子径、変動係数(CV値)、架橋度は表2に示す通りであった。
冷却管、温度計、滴下口を備えた四つ口フラスコに、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50部をイオン交換水2000部で溶解した溶液に、コア用単量体組成物(コア用ビニル単量体及びコア用シラン単量体)としてのMPTMS100部、nBMA850部、MMA850部、HEMA150部、16HXA150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」)42部を溶解した溶液を加え、懸濁させて単量体成分の懸濁液を調製した。
コア用単量体組成物の種類と使用量を表2に示す通りに変更したこと以外は合成例10(コア粒子10)と同様にして、コア粒子12を得た。さらに、目開き8μmと15μmのメッシュを用いて分級しコア粒子13を得た。コア粒子12、13の粒子径、変動係数(CV値)、架橋度は表2に示す通りであった。なお分級前の粒子径は12.84μm、変動係数(CV値)は、30.7%であった。
コア用シラン単量体、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てポリシロキサン粒子(シード粒子)を作製し、コア用ビニル単量体の種類と使用量を表2に示す通りに変更したこと以外は合成例1と同様にして、コア粒子14を得た。コア粒子14は表2に示す通りであった。
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部と、25%アンモニア水3部、メタノール600部を入れ、攪拌下、滴下口からコア用単量体成分(コア用シラン単量体)としてMPTMS(信越化学工業社製、「KBM503」)40.7部及びVTMS(信越化学工業社製、「KBM1003」)59.3部、MPTMS及びVTMSの加水分解、縮合反応を行って、メタクリロイル基及びビニル基を有するシード粒子としての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。反応開始から2時間後、得られたポリシロキサン粒子の乳濁液をサンプリングし、粒子径を測定したところ、体積平均粒子径は2.36μm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2.5部をイオン交換水50部で溶解した溶液に、コア用単量体成分(コア用ビニル単量体)としてのDVB(新日鉄住金化学社製「DVB960」)50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」)1.6部を溶解した溶液を加え、乳化分散させてコア用単量体成分(コア用ビニル単量体)を含む乳化液Aを調製した。
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0.4部をイオン交換水15部で溶解した溶液に、コア用単量体成分(コア用ビニル単量体)としてのCHMA15部を加え、乳化分散させてコア用単量体成分(コア用ビニル単量体)を含む乳化液Bを調製した。
得られた乳化液Aをポリシロキサン粒子の乳濁液に加え、一時間撹拌した後、さらに、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8.3部を加え、窒素雰囲気下で反応液を65℃まで昇温させて1時間保持した後、乳化液Bを加え、さらに窒素雰囲気下で反応液を65℃、2時間保持して、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、120℃で2時間真空乾燥させてコア粒子15を得た。コア粒子15の体積平均粒子径、変動係数(CV値)、架橋度は表2に示す通りであった。
(製造例1)
冷却管、温度計、滴下口を備えた四つ口フラスコに、メタノール525部、イオン交換水1050部、25%アンモニア水1.4部、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の20%水溶液17.5部を混合し、コア粒子1を70部分散させた後、シェル用単量体成分(シェル用シラン単量体)としてMPTMS7.0部を加え、2時間攪拌してコア粒子分散液を調製した。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の20%水溶液0.9部をイオン交換水100部で溶解した溶液に、シェル用単量体成分(シェル用ビニル単量体)としてのSt30.8部、DVB(新日鉄住金化学社製「DVB960」)4.2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」)0.4部を溶解した溶液を加え、乳化分散させたシェル用単量体成分(シェル用ビニル単量体)の乳化液をコア粒子分散液に加え1時間攪拌した後、分散助剤としてのカヤノールミーリング4GW(日本化薬社製)0.04部をイオン交換水20部に溶解した溶液を加え、窒素雰囲気下で反応液を65℃まで昇温させて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、40℃で12時間真空乾燥させて樹脂粒子(1)を得た。
表3又は表4に示す通りに、コア粒子、シェル用シラン単量体、シェル用ビニル単量体、シェル用単量体成分(シェル用ビニル単量体)の乳化液に用いた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(表中、「界面活性剤水溶液」と記載)の20%水溶液、カヤノールミーリング4GWを使用したこと以外は製造例1と同様にして、樹脂粒子(2)~(8)、(10)~(13)、(16)、(17)、(19)~(25)を得た。
冷却管、温度計、滴下口を備えた四つ口フラスコに、メタノール525部、イオン交換水1050部、25%アンモニア水1.4部、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の20%水溶液17.5部を混合し、コア粒子3を70部分散させた後、シェル用単量体成分(シェル用シラン単量体)としてVTMS14.0部を加え、2時間攪拌してコア粒子分散液を調製した。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」)0.4部をメタノール4部に溶解した溶液を加え、窒素雰囲気下で反応液を65℃まで昇温させて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、40℃で12時間真空乾燥させて樹脂粒子(9)を得た。
コア粒子として表3に示す通りのコア粒子を使用し、シェル用シラン単量体として、表3に示す通りのモノマー種を表3に示す通りの使用量で使用したこと以外は製造例9と同様にして、樹脂粒子(14)、(15)、(18)を得た。
冷却管、温度計、滴下口を備えた四つ口フラスコに、エタノール80部、イオン交換水30部、ポリピニルピロリドン((和光純薬工業社製、「PVP K-30」)3.6部を混合し、コア粒子2を30部分散させた後、2,2’-アゾビス(2-メチルブチロニトリル)(和光純薬工業社製、「V-59」)0.03部、NPGDMA0.6部、St2.4部を混合した溶液を加え、窒素雰囲気下で反応液を70℃まで昇温させて5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、40℃で12時間真空乾燥させて樹脂粒子(26)を得た。
コア粒子として表4に示す通りのコア粒子を使用したこと以外は、製造例26と同様にして、樹脂粒子(27)を得た。
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部、St95部、MAA5部を加え混合した溶液を窒素雰囲気下で70℃まで昇温させた後、過硫酸アンモニウム0.8部とイオン交換水100部を混合した溶液を投入し、8時間単量体成分のラジカル重合をした。ラジカル重合後の乳濁液をスプレードライにて粉体化し、300nmの子粒子を得た。得られた子粒子10部とコア粒子9100部をハイブリダイゼーションにて複合化し、樹脂粒子(28)を得た。
冷却管、温度計、滴下口を備えた四つ口フラスコに、メタノール364部、イオン交換水1456部、25%アンモニア水4.4部、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の20%水溶液17.5部を混合し、コア粒子14を70部分散させた後、シェル用単量体成分(シェル用シラン単量体)としてMPTMS14.0部を加え、2時間攪拌してコア粒子分散液を調製した。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の20%水溶液0.2部をイオン交換水100部で溶解した溶液に、シェル用単量体成分(シェル用ビニル単量体)としてのDVB(新日鉄住金化学社製「DVB960」)7.0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」)2.1部を溶解した溶液を加え、乳化分散させたシェル用単量体成分(シェル用ビニル単量体)の乳化液をコア粒子分散液に加え1時間攪拌した後、ポリビニルアルコールの10%水溶液21.0部に溶解した溶液を加え、窒素雰囲気下で反応液を65℃まで昇温させて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、80℃で4時間真空乾燥させて樹脂粒子(29)を得た。
コア粒子として表4に示す通りのコア粒子を使用し、シェル用シラン単量体として、表4に示す通りのモノマー種を表4に示す通りの使用量で使用し、シェル用ビニル単量体として、表Xに示す通りのモノマー種を表4に示す通りの使用量で使用し、乾燥を窒素雰囲気下280℃で1時間の焼成処理に変更したこと以外は製造例29と同様にして、樹脂粒子(30)を得た。
また、得られた樹脂粒子(1)~(30)について、体積平均粒子径、変動係数(CV値)、凸部の個数密度、凸部の平均高さ、凸部の平均底辺直径、凸部の高さと底辺の比(高さ/底辺)、凸部の高さと樹脂粒子の堆積平均粒子径の比(高さ/樹脂粒子径)、凸部の高さと凸部の底辺の積(高さ×底辺)、樹脂粒子1個当たりの凸部の個数、球状部の表面積1μm2あたりの凸部の個数(凸部密度)、球状部の表面積(球状部表面積)、凸部を球状部に対する液滴と仮定したときの接触角(接触角)、突起脱落試験、周縁部の融点測定の結果を表3、4に示す。
基材とする樹脂粒子に、水酸化ナトリウム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ることによりセンシタイジングし、次いで二塩化パラジウム溶液に浸漬させることによりアクチベーティングする方法(センシタイジング-アクチベーション法)によって、パラジウム核を形成させた。次に、パラジウム核を形成させた樹脂粒子2部をイオン交換水400部に添加し、超音波分散処理を行った後、得られた樹脂粒子懸濁液を70℃の温浴で加温した。このように懸濁液を加温した状態で、別途70℃に加温した無電解めっき液(日本カニゼン(株)製「シューマーS680」)600部を加えることにより、無電解ニッケルめっき反応を生じさせた。水素ガスの発生が終了したことを確認した後、固液分離を行い、イオン交換水、メタノールの順で洗浄し、100℃で2時間真空乾燥して、ニッケルめっきを施した粒子を得た。次いで、得られたニッケルめっき粒子を、シアン化金カリウムを含有する置換金めっき液に加え、ニッケル層表面にさらに金めっきを施すことにより、導電性微粒子を得た。
得られた導電性微粒子について、基材粒子(樹脂粒子)の凸部の接触角、導電性金属層の膜厚、及び導電性評価の結果は表5に示すとおりであった。
2a 周縁部
2b 周縁層
3 凸部
4 三角形
5 三角形の底辺
6a,6b 凸部の起点
8 凸部の頂部
9a 凸部側の接線
9b 周縁層側の接線
10 境界線
Claims (10)
- 球状部とその表面に形成された複数の凸部を有する周縁部とから構成される樹脂粒子であって、
前記球状部及び周縁部は、ビニル重合体及び/又はポリシロキサン成分で形成され、
球状部と周縁部とは組成が異なり
周縁部の融点は200℃以上であり、かつ
樹脂粒子の断面を透過型電子顕微鏡で観察したときの前記周縁部と球状部の間の境界線の曲率中心が球状部に存在する樹脂粒子。 - 凸部の平均高さが0.05μm以上、5μm以下である請求項1に記載の樹脂粒子。
- 凸部の平均底辺直径が0.1μm以上、10μm以下である請求項1又は2に記載の樹脂粒子。
- 凸部の個数密度が、0.01個/μm2以上、10個/μm2以下である請求項1~3のいずれか一項に記載の樹脂粒子。
- 体積平均粒子径が1μm以上、50μm以下である請求項1~4のいずれか一項に記載の樹脂粒子。
- 樹脂粒子1個当たりの凸部の個数が5個以上、5000個以下である請求項1~5のいずれか一項に記載の樹脂粒子。
- 前記凸部の接触角が平均で90°以下である請求項1~6のいずれか一項に記載の樹脂粒子。
- 前記樹脂粒子がコアとシェルで構成されるコア-シェル構造を有するものであり、前記コアは前記球状部を含み、前記シェルは前記周縁部を含むものである請求項1~7のいずれか一項に記載の樹脂粒子。
- 請求項1~8のいずれかに記載の樹脂粒子と、該樹脂粒子の表面凸部をこの凸部形状に沿って被覆する導電性金属層とを有する導電性微粒子。
- 請求項9に記載の導電性微粒子を含む異方性導電材料。
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