WO2018230470A1 - Resin particles, conductive particles, conductive material, adhesive, connection structure and liquid crystal display element - Google Patents

Resin particles, conductive particles, conductive material, adhesive, connection structure and liquid crystal display element Download PDF

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Publication number
WO2018230470A1
WO2018230470A1 PCT/JP2018/022071 JP2018022071W WO2018230470A1 WO 2018230470 A1 WO2018230470 A1 WO 2018230470A1 JP 2018022071 W JP2018022071 W JP 2018022071W WO 2018230470 A1 WO2018230470 A1 WO 2018230470A1
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Prior art keywords
resin particles
conductive
resin
particles
particle
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PCT/JP2018/022071
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French (fr)
Japanese (ja)
Inventor
啓太 有村
恭幸 山田
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2018534195A priority Critical patent/JPWO2018230470A1/en
Priority to KR1020197016800A priority patent/KR102391136B1/en
Priority to CN201880030153.7A priority patent/CN110603272A/en
Publication of WO2018230470A1 publication Critical patent/WO2018230470A1/en

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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

Definitions

  • the present invention relates to resin particles formed of a resin.
  • the present invention also relates to conductive particles, conductive materials, adhesives, connection structures and liquid crystal display elements using the resin particles.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder.
  • the anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing.
  • connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip.
  • conductive particles conductive particles having resin particles and conductive portions arranged on the surface of the resin particles may be used.
  • the liquid crystal display element is configured by arranging liquid crystal between two glass substrates.
  • a spacer is used as a gap control material in order to keep the distance (gap) between two glass substrates uniform and constant.
  • resin particles are generally used as the spacer.
  • Patent Document 1 discloses conductive particles having polymer particles and a conductive layer covering the surface of the polymer particles.
  • the polymer particle is composed of at least one polyfunctional (meth) acrylate selected from a bifunctional (meth) acrylate monomer, a trifunctional (meth) acrylate monomer, and a tetrafunctional (meth) acrylate monomer, and a monofunctional It is obtained by copolymerizing a copolymerization component containing the (meth) acrylate monomer.
  • the bifunctional (meth) acrylate monomer is 1,10-decandiol di (meth) acrylate.
  • the copolymerization component has the above-mentioned single-tube ability with respect to 100 parts by weight of the bifunctional (meth) acrylate monomer.
  • a (meth) acrylate monomer is contained in the range of 10 to 400 parts by weight.
  • the copolymer component includes the tetrafunctional (meth) acrylate monomer and the monofunctional (meth) acrylate monomer.
  • the above-mentioned single-capacity (meth) acrylate monomer is contained at 80% by weight or less.
  • the compression deformation recovery rate of the polymer particles is 70% or more.
  • the volume expansion coefficient of the polymer particles is 1.3 or less.
  • Patent Document 2 discloses highly resilient resin particles composed of a crosslinked (meth) acrylic ester resin.
  • the average particle size of the highly restorable resin particles is 1 ⁇ m to 100 ⁇ m.
  • the restoration rate of the highly restoring resin particles is 22% or more.
  • 30% compressive strength of the high resilience resin particles is 1.5kgf / mm 2 ⁇ 5.0kgf / mm 2.
  • a conductive material containing conductive particles and a binder and an adhesive containing a spacer and a binder may be exposed to a heating environment during use, and the binder may be cured and shrunk.
  • Conventional resin particles may not shrink sufficiently upon heating and may not be able to follow the curing shrinkage of the binder. As a result, floating or peeling may occur between the conductive material and the electrode or between the adhesive and the liquid crystal display element member or the like.
  • a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, two or more polymerizable functional groups, and having a cyclic organic group
  • the polymer is a polymer with a second polymerizable compound, and the weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more.
  • a resin particle in which, when the resin particle is heated at 150 ° C. for 1000 hours, the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating is 0.9 or less.
  • the compression recovery rate when compressed and deformed by 60% is 10% or less.
  • the 10% K value is 3000 N / mm 2 or less.
  • the 30% K value is 1500 N / mm 2 or less.
  • the ratio of the 30% K value of the heated resin particle to the 30% K value of the resin particle before heating is 0.8 to 1.5.
  • the cyclic organic group in the first polymerizable compound and the cyclic organic group in the second polymerizable compound are each a hydrocarbon group.
  • the cyclic organic group in the first polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group.
  • the cyclic organic group in the second polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group.
  • the resin particle contains an acid phosphate compound.
  • the resin particle is used as a spacer, or a conductive part is formed on the surface and used to obtain conductive particles having the conductive part.
  • a conductive particle comprising the resin particle described above and a conductive part disposed on the surface of the resin particle.
  • a conductive material including conductive particles and a binder, wherein the conductive particles include the resin particles described above and a conductive portion disposed on a surface of the resin particles.
  • an adhesive containing the above-described resin particles and a binder.
  • a first connection target member having a first electrode on the surface
  • a second connection target member having a second electrode on the surface
  • the first connection target member A connecting portion connecting the second connection target member, wherein the material of the connecting portion includes the resin particles described above, and the first electrode and the second electrode are the connecting portion.
  • the first liquid crystal display element member the second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member
  • a liquid crystal display element including a spacer disposed between the spacers, the spacer being the resin particles described above.
  • the resin particles according to the present invention include a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and two or more polymerizable functional groups and having a cyclic organic group. 2 is a polymer with a polymerizable compound.
  • the weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more.
  • the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating is 0.9 or less. Since the resin particles according to the present invention have the above-described configuration, the occurrence of springback can be effectively suppressed, and the occurrence of floating or peeling can be effectively suppressed.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention.
  • FIG. 5 is a cross-sectional view showing an example of a connection structure using the resin particles according to the present invention.
  • FIG. 6 is a cross-sectional view showing an example of a liquid crystal display element using the resin particles according to the present invention as a spacer for a liquid crystal display element.
  • the resin particles according to the present invention include a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and two or more polymerizable functional groups and having a cyclic organic group. 2 is a polymer with a polymerizable compound.
  • the weight ratio (WM / W) of the content (WM) derived from the first polymerizable compound to the content (WD) derived from the second polymerizable compound. WD) is 7 or more.
  • the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating is 0.9 or less.
  • the occurrence of springback can be effectively suppressed, and the occurrence of floating or peeling can be effectively suppressed.
  • the compression recovery rate is relatively low, the action of the compressed resin particles trying to return to the original shape is relatively difficult, and a springback occurs. It is hard to do.
  • the resin particles according to the present invention are used as conductive particles, a decrease in the contact area between the conductive particles and the electrodes can be effectively prevented, and the conduction reliability between the electrodes can be effectively reduced. Can be increased.
  • the spacer can be sufficiently brought into contact with a liquid crystal display element member and the like, and the gap can be controlled with higher accuracy.
  • a conductive material containing conductive particles and a binder and an adhesive containing a spacer and a binder may be exposed to a heating environment during use, and the binder may be cured and shrunk by heating. Since the resin particles according to the present invention have the above-described configuration, the resin particles shrink relatively easily by heating. Since the particle diameter of the resin particles after heating is appropriately smaller than the particle diameter of the resin particles before heating, the resin particles can follow the curing shrinkage of the binder. As a result, it is possible to effectively suppress the occurrence of floating or peeling between the conductive material and the electrode, or between the adhesive and the liquid crystal display element member.
  • the weight ratio (WM / W) of the content (WM) derived from the first polymerizable compound to the content (WD) derived from the second polymerizable compound. WD) is 7 or more. From the viewpoint of more effectively suppressing the occurrence of springback and further effectively suppressing the occurrence of floating or peeling, the weight ratio (WM / WD) is preferably 9 or more, more preferably It is 13 or more, preferably 20 or less, more preferably 17 or less.
  • the following methods may be mentioned as methods for determining the content (WM) derived from the first polymerizable compound and the content (WD) derived from the second polymerizable compound. From the blended amount of the first and second polymerizable compounds used in obtaining the polymer and the remaining amount of the first and second polymerizable compounds after polymerization, the polymerized first and second polymerizable compounds The amount is determined and calculated from the amount of the first and second polymerizable compounds polymerized.
  • the following methods are used as a method for obtaining the content (WM) of the structure derived from the first polymerizable compound and the content (WD) of the structure derived from the second polymerizable compound from the resin particles. Can be mentioned.
  • the amount of functional groups in the respective resin particles of the first and second polymerizable compounds used when obtaining the polymer, and the respective resins of the first and second polymerizable compounds used when obtaining the polymer It calculates from the quantity of the group which the functional group in particle
  • the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating is 0.9 or less.
  • the above ratio is preferably 0.4 or more, more preferably It is 0.6 or more, preferably 0.85 or less, more preferably 0.8 or less.
  • the particle size of the resin particles (the particle size of the resin particles before heating) can be appropriately set depending on the application.
  • the particle diameter of the resin particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less, particularly preferably. 50 ⁇ m or less.
  • the particle diameter of the resin particles is not less than the above lower limit and not more than the above upper limit, the occurrence of springback can be more effectively suppressed, and the occurrence of floating or peeling can be further effectively suppressed. be able to.
  • the resin particles can be suitably used for conductive particles.
  • the particle diameter of the resin particles is 0.5 ⁇ m or more and 500 ⁇ m or less, the resin particles can be suitably used for spacer applications.
  • the particle diameter of the resin particles indicates the diameter when the resin particles are spherical, and the resin particles are not spherical. Shows the maximum diameter.
  • the particle size of the resin particles (the particle size of the resin particles before heating and the particle size of the resin particles after heating) is preferably an average particle size, and more preferably a number average particle size.
  • the particle diameter of the resin particles is determined using a particle size distribution measuring device or the like.
  • a particle size distribution measuring apparatus using principles such as laser scattered light, electrical resistance value change, and image analysis after imaging can be used.
  • the particle size of about 100,000 resin particles is measured, and the average value is measured.
  • the method etc. of calculating are mentioned.
  • the particle diameter of the resin particles is preferably obtained by observing 50 arbitrary resin particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the particle diameter of the resin particles in the conductive particles, for example, it can be measured as follows.
  • An embedded resin for inspecting conductive particles is prepared by adding to and dispersing in “Technobit 4000” manufactured by Kulzer so that the content of the conductive particles is 30% by weight.
  • a cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the conductive particles dispersed in the embedding resin for inspection.
  • IM4000 manufactured by Hitachi High-Technologies Corporation
  • FE-SEM field emission scanning electron microscope
  • the coefficient of variation (CV value) of the particle diameter of the resin particles is preferably 0. 0.5% or more, more preferably 1% or more, preferably 10% or less, more preferably 7% or less.
  • the resin particles can be suitably used for spacers and conductive particles.
  • the coefficient of variation of the particle diameter of the resin particles may be less than 0.5%.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : standard deviation of particle diameter of resin particles Dn: average value of particle diameter of resin particles
  • the shape of the resin particles is not particularly limited.
  • the resin particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
  • 10% K value of the resin particles is preferably 1000 N / mm 2 or more, more preferably 1500 N / mm 2 or more, preferably 3000N / mm 2 or less, more preferably 2750N / mm 2 or less, more preferably 2500N / mm 2 or less.
  • the 10% K value of the resin particles is not less than the above lower limit and not more than the above upper limit, the occurrence of spring back can be more effectively suppressed, and the occurrence of floating or peeling can be more effectively achieved. Can be suppressed.
  • 30% K value of the resin particles is preferably 300N / mm 2 or more, more preferably 500 N / mm 2 or more, preferably 1500 N / mm 2 or less, more preferably 1200 N / mm 2 or less, more preferably 1000 N / mm 2 or less.
  • the 30% K value of the resin particles is not less than the above lower limit and not more than the above upper limit, the occurrence of spring back can be more effectively suppressed, and the occurrence of floating or peeling can be more effectively achieved. Can be suppressed.
  • the 30% K value of the resin particles is preferably 0.8 or more, more preferably 1.15 or more, and still more preferably 1.2 or more.
  • the 30% K value of the resin particles is preferably 1.5 or less, more preferably 1.45 or less, and still more preferably 1.4 or less.
  • the ratio (30% K value of the heated resin particles / 30% K value of the resin particles before heating) is not less than the above lower limit and not more than the above upper limit, the occurrence of springback is more effectively suppressed. And the occurrence of floating or peeling can be more effectively suppressed.
  • the 10% K value and 30% K value compression elastic modulus when the resin particles are compressed by 10% and compression elastic modulus when the resin particles are compressed by 30%
  • compression elastic modulus when the resin particles are compressed by 30% can be measured as follows.
  • one resin particle is compressed on a smooth indenter end face of a cylinder (diameter 100 ⁇ m, made of diamond) at 25 ° C. under conditions of a compression rate of 0.3 mN / sec and a maximum test load of 20 mN. .
  • the load value (N) and compression displacement (mm) at this time are measured.
  • a 10% K value or a 30% K value at 25 ° C. can be obtained by the following formula.
  • the above-mentioned micro compression tester for example, “Micro compression tester MCT-W200” manufactured by Shimadzu Corporation, “Fischer Scope H-100” manufactured by Fisher, etc. are used.
  • the 10% K value or 30% K value of the resin particles is preferably calculated by arithmetically averaging the 10% K value or 30% K value of 50 resin particles selected arbitrarily.
  • the above K value represents the hardness of the resin particles universally and quantitatively. By using the K value, the hardness of the resin particles can be expressed quantitatively and uniquely.
  • the compression recovery rate when the resin particles are subjected to 60% compression deformation is preferably It is 2% or more, more preferably 4% or more, preferably 10% or less, more preferably 9.5% or less, and further preferably 9% or less.
  • the compression recovery rate when the resin particles are 60% compressed and deformed can be measured as follows.
  • the resin particle is compressed and deformed by 60% in the center direction of the resin particle at 25 ° C. on a smooth indenter end face of a cylinder (diameter 100 ⁇ m, made of diamond) using a micro compression tester. Apply a load (reverse load value). Thereafter, unloading is performed up to the origin load value (0.40 mN). The load-compression displacement during this period is measured, and the compression recovery rate when 60% compression deformation at 25 ° C. is obtained from the following equation. The load speed is 0.33 mN / sec.
  • the above-mentioned micro compression tester for example, “Micro compression tester MCT-W200” manufactured by Shimadzu Corporation, “Fischer Scope H-100” manufactured by Fisher, etc. are used.
  • Compression recovery rate (%) [L2 / L1] ⁇ 100
  • L1 Compressive displacement from the origin load value to the reverse load value when applying a load
  • L2 Unloading displacement from the reverse load value to the origin load value when releasing the load
  • the use of the resin particles is not particularly limited.
  • the resin particles are suitably used for various applications.
  • the resin particles are preferably used as spacers or to obtain conductive particles having a conductive part.
  • the conductive portion is formed on the surface of the resin particle.
  • the resin particles are preferably used as spacers.
  • the resin particles are preferably used for obtaining conductive particles having a conductive part.
  • Examples of the method of using the spacer include a liquid crystal display element spacer, a gap control spacer, and a stress relaxation spacer.
  • the above spacer for gap control is used for gap control of laminated chips for ensuring standoff height and flatness, and for optical component gap control for ensuring smoothness of the glass surface and thickness of the adhesive layer.
  • the stress relaxation spacer can be used for stress relaxation of a sensor chip or the like, and stress relaxation of a connection portion connecting two connection target members.
  • the resin particles are preferably used as spacers for liquid crystal display elements, and are preferably used as peripheral sealing agents for liquid crystal display elements.
  • the resin particles preferably function as a spacer. Since the resin particles have good compressive deformation characteristics, the resin particles are used as spacers to be arranged between the substrates, or conductive parts are formed on the surface and used as conductive particles to electrically connect the electrodes. In such a case, spacers or conductive particles are efficiently disposed between the substrates or the electrodes. Furthermore, in the resin particles, since damage to the liquid crystal display element member and the like can be suppressed, connection failure in the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles. And display defects are less likely to occur.
  • the resin particles are also suitably used as an inorganic filler, a toner additive, a shock absorber or a vibration absorber.
  • the resin particles can be used as a substitute for rubber or a spring.
  • the resin particles according to the present invention include a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and two or more polymerizable functional groups and having a cyclic organic group. 2 is a polymer with a polymerizable compound.
  • the resin particles are preferably obtained by polymerizing the first polymerizable compound and the second polymerizable compound.
  • the resin particles have a central portion of the resin particles and a surface portion of the resin particles. It is preferable that they are composed of the same polymer.
  • the compounding ratio of the polymerizable compound in the central part of the resin particles and the compounding ratio of the polymerizable compound in the surface part of the resin particles may be the same or different.
  • the constituent ratio of the constituent components in the central portion of the resin particles and the constituent ratio of the constituent components in the surface portion of the resin particles may be the same or different.
  • the center part of the resin particles is formed of the center part forming material, and the surface part of the resin particles is formed of the surface part forming material.
  • the component of the center portion forming material and the surface portion forming material are used. These components are preferably the same.
  • the component ratio of the central portion forming material and the component ratio of the surface portion forming material may be the same or different.
  • the resin particle it is preferable that the resin particle has a region including the center portion forming material and not including the surface portion forming material or including the surface portion forming material in less than 25% in the center portion. In the resin particle, it is preferable that the resin particle has a region including the surface portion forming material and not including the center portion forming material or including the center portion forming material in less than 25% in the surface portion.
  • the resin particle is preferably not a core-shell particle including a core and a shell disposed on the surface of the core, and preferably does not have an interface between the core and the shell in the resin particle.
  • the resin particles preferably do not have an interface in the resin particles, and more preferably do not have an interface in which different surfaces are in contact with each other.
  • the resin particles preferably do not have a discontinuous portion where a surface exists, and preferably do not have a discontinuous portion where a structural surface exists.
  • the first polymerizable compound has one polymerizable functional group (first polymerizable functional group).
  • the polymerizable functional group (first polymerizable functional group) is not particularly limited, and examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group.
  • Examples of the first polymerizable compound include styrene, phenyl methacrylate, phenyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, and isobornyl acrylate.
  • the said 1st polymeric compound only 1 type may be used and 2 or more types may be used together.
  • the second polymerizable compound has two or more polymerizable functional groups (second polymerizable functional groups).
  • the polymerizable functional group (second polymerizable functional group) is not particularly limited, and examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group.
  • examples of the second polymerizable compound include divinylbenzene, divinylnaphthalene, divinylcyclohexane, and trivinylcyclohexane.
  • the said 2nd polymeric compound only 1 type may be used and 2 or more types may be used together.
  • the resin particles preferably have a weight ratio of the first polymerizable compound and the second polymerizable compound (weight of the first polymerizable compound / weight of the second polymerizable compound), preferably 7 or more. More preferably, it is more preferably 9 or more, further preferably 13 or more, preferably 20 or less, more preferably 18.5 or less, and still more preferably 17 or less.
  • the resin particles are preferably obtained by polymerizing the first polymerizable compound and the second polymerizable compound at a weight ratio of 7 or more, more preferably 9 or more. It is more preferable to obtain the polymer by the above.
  • the resin particles are preferably obtained by polymerizing the first polymerizable compound and the second polymerizable compound at a weight ratio of 20 or less, more preferably 18.5 or less. More preferably, it is obtained by polymerization at 17 or less.
  • the resin particles are obtained by polymerizing the first polymerizable compound and the second polymerizable compound at a weight ratio in the above preferable range, thereby more effectively suppressing the occurrence of springback. And the occurrence of floating or peeling can be more effectively suppressed.
  • the resin particles according to the present invention preferably contain two or more kinds of cyclic organic groups.
  • the first polymerizable compound has a cyclic organic group (first cyclic organic group).
  • the first polymerizable compound has one or more cyclic organic groups.
  • the second polymerizable compound has a cyclic organic group (second cyclic organic group).
  • the second polymerizable compound has one or more cyclic organic groups.
  • the cyclic organic group (first cyclic organic group) in the first polymerizable compound and the cyclic organic group (second cyclic organic group) in the second polymerizable compound are the same. May be different. It is preferable that the cyclic organic group (first cyclic organic group) in the first polymerizable compound and the cyclic organic group (second cyclic organic group) in the second polymerizable compound are different.
  • a cyclic organic group (first cyclic organic group) in the first polymerizable compound is used.
  • the cyclic organic group (second cyclic organic group) in the second polymerizable compound are each preferably a hydrocarbon group.
  • hydrocarbon group examples include a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, a cyclopropyl group, a cyclohexyl group, an isobornyl group, and a dicyclopentanyl group.
  • the resin particles according to the present invention have a phenylene group, a cyclohexyl group or an isobornyl group. It is preferable to have two or more cyclic organic groups.
  • a cyclic organic group (first cyclic organic group) in the first polymerizable compound is used.
  • a cyclic organic group (second cyclic organic group) in the second polymerizable compound is used.
  • the resin particles preferably contain an acid phosphate compound from the viewpoint of further effectively improving the adhesion between the resin particles and the plating.
  • the resin particles preferably have a phosphoric acid structure derived from an acid phosphate compound on the surface.
  • the adhesion with the plating can be further effectively improved.
  • plating cracks can be more effectively suppressed even when the resin particles shrink due to heating.
  • the conductive material is heated when the electrodes are connected, or the conductive material is exposed to a heating environment. Even if it does, a plating crack can be suppressed still more effectively and the connection reliability between electrodes can be improved much more effectively.
  • the resin particles preferably contain an acid phosphate compound.
  • the resin particles preferably have a phosphoric acid structure derived from an acid phosphate compound on the surface.
  • the acid phosphate compound is preferably an acidic phosphate compound.
  • the acid phosphate compound examples include ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxy acid phosphate
  • examples thereof include ethyl methacrylic acid phosphate, dibutyl acid phosphate, and bis (2-ethylhexyl) acid phosphate.
  • the said acid phosphate compound only 1 type may be used and 2 or more types may be used together.
  • the content of the acid phosphate compound in 100% by weight of the resin particles is preferably 1% by weight or more, more preferably 5% by weight or more. And preferably 20% by weight or less, more preferably 15% by weight or less.
  • the electroconductive particle which concerns on this invention is equipped with the resin particle mentioned above and the electroconductive part arrange
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • the conductive part 1 has resin particles 11 and a conductive portion 2 disposed on the surface of the resin particles 11.
  • the conductive part 2 is in contact with the surface of the resin particle 11.
  • the conductive part 2 covers the surface of the resin particle 11.
  • the conductive particle 1 is a coated particle in which the surface of the resin particle 11 is covered with the conductive part 2.
  • the conductive part 2 is a single-layer conductive part (conductive layer).
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • the conductive part 22 has resin particles 11 and conductive portions 22 arranged on the surface of the resin particles 11.
  • the conductive part 22 as a whole has a first conductive part 22A on the resin particle 11 side and a second conductive part 22B on the opposite side to the resin particle 11 side.
  • the first conductive portion 22A and the second conductive portion 22B may be formed as different conductive portions or may be formed as the same conductive portion.
  • the first conductive part 22 ⁇ / b> A is disposed on the surface of the resin particle 11.
  • a first conductive portion 22A is disposed between the resin particle 11 and the second conductive portion 22B.
  • the first conductive portion 22 ⁇ / b> A is in contact with the resin particle 11.
  • the second conductive portion 22B is in contact with the first conductive portion 22A.
  • the first conductive portion 22A is disposed on the surface of the resin particle 11, and the second conductive portion 22B is disposed on the surface of the first conductive portion 22A.
  • FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
  • the 3 includes resin particles 11, a conductive portion 32, a plurality of core materials 33, and a plurality of insulating materials 34.
  • the conductive portion 32 is disposed on the surface of the resin particle 11.
  • the plurality of core substances 33 are arranged on the surface of the resin particles 11.
  • the conductive portion 32 is disposed on the surface of the resin particle 11 so as to cover the resin particle 11 and the plurality of core substances 33.
  • the conductive portion 32 is a single-layer conductive portion (conductive layer).
  • the conductive particles 31 have a plurality of protrusions 31a on the outer surface.
  • the conductive portion 32 has a plurality of protrusions 32a on the outer surface.
  • the plurality of core materials 33 raise the outer surface of the conductive portion 32. Since the outer surface of the conductive portion 32 is raised by a plurality of core materials 33, the protrusions 31a and 32a are formed.
  • the plurality of core materials 33 are embedded in the conductive portion 32.
  • a core substance 33 is disposed inside the protrusions 31a and 32a.
  • a plurality of core materials 33 are used to form the protrusions 31a and 32a.
  • a plurality of the core substances may not be used to form the protrusions.
  • the conductive particles may not include a plurality of the core substances.
  • the conductive particles 31 have an insulating substance 34 disposed on the outer surface of the conductive portion 32. At least a part of the outer surface of the conductive portion 32 is covered with an insulating material 34.
  • the insulating substance 34 is made of an insulating material and is an insulating particle.
  • the electroconductive particle which concerns on this invention may have the insulating substance arrange
  • the conductive particles do not necessarily have an insulating material.
  • the conductive particles may not include a plurality of insulating substances.
  • the metal for forming the conductive part is not particularly limited.
  • the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and tungsten. , Molybdenum, and alloys thereof.
  • the metal include tin-doped indium oxide (ITO) and solder. Since the connection resistance between the electrodes can be further reduced, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.
  • the conductive portion and the outer surface portion of the conductive portion contain nickel.
  • the content of nickel in 100% by weight of the conductive part containing nickel is preferably 10% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, particularly preferably. Is 90% by weight or more.
  • the content of nickel in 100% by weight of the conductive part containing nickel may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.
  • hydroxyl groups are present on the surface of the conductive part due to oxidation.
  • a hydroxyl group exists on the surface of a conductive portion formed of nickel by oxidation.
  • An insulating substance can be disposed on the surface of the conductive part having such a hydroxyl group (the surface of the conductive particle) through a chemical bond.
  • the conductive part may be formed of a single layer.
  • the electroconductive part may be formed of the some layer. That is, the conductive part may have a laminated structure of two or more layers.
  • the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable.
  • the outermost layer is such a preferable conductive portion, the connection resistance between the electrodes can be further effectively reduced. Further, when the outermost layer is a gold layer, the corrosion resistance can be further effectively improved.
  • the method for forming the conductive part on the surface of the resin particles is not particularly limited.
  • Examples of the method for forming the conductive part include a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of resin particles with a metal powder or a paste containing a metal powder and a binder. Etc. Since formation of the conductive part is simple, a method by electroless plating is preferred.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
  • the particle diameter of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, Particularly preferably, it is 20 ⁇ m or less.
  • the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes becomes sufficiently large, and Aggregated conductive particles are hardly formed when the conductive portion is formed.
  • the interval between the electrodes connected via the conductive particles does not become too large, and the conductive portion is difficult to peel from the surface of the resin particles.
  • the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of a conductive material.
  • the particle diameter of the conductive particles indicates the diameter when the conductive particles are true spherical, and indicates the maximum diameter when the conductive particles are not true spherical.
  • the particle diameter of the conductive particles is preferably an average particle diameter, and more preferably a number average particle diameter.
  • the particle diameter of the conductive particles is, for example, observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or a measurement result obtained by a plurality of laser diffraction particle size distribution measuring devices. It is calculated
  • the thickness of the conductive part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently bonded at the time of connection between the electrodes. Deform.
  • the thickness of the conductive part of the outermost layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably Is 0.1 ⁇ m or less.
  • the thickness of the conductive portion of the outermost layer is not less than the above lower limit and not more than the above upper limit, the coating by the conductive portion of the outermost layer becomes uniform, corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficient It becomes low.
  • the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.
  • the thickness of the conductive part can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the thickness of the conductive part it is preferable to calculate the average value of the thickness of five places of arbitrary electroconductive parts as the thickness of the electroconductive part of one electroconductive particle, and the average value of the thickness of the whole electroconductive part is 1 piece. It is more preferable to calculate the thickness of the conductive part.
  • the thickness of the conductive portion is preferably obtained by calculating an average value of 10 arbitrary conductive particles.
  • the conductive particles preferably have a plurality of protrusions on the outer surface of the conductive part. Since the conductive particles have a plurality of protrusions on the outer surface of the conductive part, the conduction reliability between the electrodes can be further improved.
  • An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the surface of the conductive part of the conductive particles.
  • the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the conductive particles and the electrodes are separated by protrusions of the conductive particles. Insulating substances and binder resins are effectively eliminated. For this reason, the conduction
  • the core substance By embedding the core substance in the conductive part, a plurality of protrusions can be easily formed on the outer surface of the conductive part.
  • the core substance is not necessarily used in order to form the protrusion on the surface of the conductive portion of the conductive particle.
  • a method of forming the protrusion after a core material is attached to the surface of the resin particle, a method of forming a conductive part by electroless plating, and after forming a conductive part by electroless plating on the surface of the resin particle, Examples include a method of attaching a core substance and further forming a conductive portion by electroless plating.
  • a core substance is disposed on the first conductive portion, and then the second conductive portion is formed.
  • Examples thereof include a forming method and a method of adding a core substance in the middle of forming a conductive portion (such as a first conductive portion or a second conductive portion) on the surface of the resin particle. Further, in order to form the protrusion, the conductive material is formed on the resin particles by electroless plating without using the core material, and then plating is deposited on the surface of the conductive portion in a protruding shape, and further, by electroless plating. A method of forming a conductive portion or the like may be used.
  • the core substance is added to the dispersion of resin particles, and the core substance is accumulated on the surface of the resin particles by van der Waals force and adhered.
  • a method of adding a core substance to a container containing resin particles and attaching the core substance to the surface of the resin particles by a mechanical action such as rotation of the container Since it is easy to control the amount of the core material to be attached, a method in which the core material is accumulated on the surface of the resin particles in the dispersion and attached is preferable.
  • the material of the core substance is not particularly limited.
  • Examples of the material of the core substance include a conductive substance and a non-conductive substance.
  • Examples of the conductive substance include metals, metal oxides, conductive non-metals such as graphite, and conductive polymers.
  • Examples of the conductive polymer include polyacetylene.
  • Examples of the non-conductive substance include silica, alumina, barium titanate, zirconia, and the like.
  • a metal is preferable because conductivity can be increased and connection resistance can be effectively reduced.
  • the core substance is preferably metal particles. As the metal that is the material of the core substance, the metals mentioned as the metal for forming the conductive part can be used as appropriate.
  • the conductive particles preferably include an insulating material disposed on the surface of the conductive part.
  • an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes.
  • the insulating material between the conductive portion of the conductive particles and the electrode can be easily removed by pressurizing the conductive particles with the two electrodes when connecting the electrodes.
  • the conductive particles have a plurality of protrusions on the outer surface of the conductive part, the insulating substance between the conductive part of the conductive particles and the electrode can be more easily removed.
  • the insulating substance is preferably an insulating particle because the insulating substance can be more easily removed during crimping between the electrodes.
  • the insulating material examples include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, thermosetting resins, water-soluble resins, and the like. Is mentioned. Only 1 type may be used for the material of the said insulating substance, and 2 or more types may be used together.
  • Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer.
  • Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polydodecyl (meth) acrylate, and polystearyl (meth) acrylate.
  • Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof.
  • Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers.
  • thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
  • crosslinking of the thermoplastic resin include introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate and the like.
  • water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose.
  • chain transfer agent for adjustment of a polymerization degree. Examples of the chain transfer agent include thiol and carbon tetrachloride.
  • a method of disposing an insulating substance on the surface of the conductive part there are a chemical method, a physical or mechanical method, and the like.
  • the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method.
  • the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition.
  • a method of disposing the insulating substance on the surface of the conductive part via a chemical bond is preferable because the insulating substance is difficult to be detached.
  • the outer surface of the conductive part and the surface of the insulating substance may each be coated with a compound having a reactive functional group.
  • the outer surface of the conductive part and the surface of the insulating substance may not be directly chemically bonded, but may be indirectly chemically bonded by a compound having a reactive functional group.
  • the carboxyl group may be chemically bonded to a functional group on the surface of the insulating substance via a polymer electrolyte such as polyethyleneimine.
  • the conductive material according to the present invention includes the above-described conductive particles and a binder.
  • the conductive particles are preferably used by being dispersed in a binder, and are preferably used as a conductive material by being dispersed in a binder.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection between electrodes.
  • the conductive material is preferably a conductive material for circuit connection.
  • the above binder is not particularly limited.
  • a known insulating resin is used as the binder.
  • the binder preferably includes a thermoplastic component (thermoplastic compound) or a curable component, and more preferably includes a curable component.
  • the curable component include a photocurable component and a thermosetting component. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator.
  • the thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
  • binder examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder, only 1 type may be used and 2 or more types may be used together.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
  • examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin.
  • examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin.
  • the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
  • the curable resin may be used in combination with a curing agent.
  • thermoplastic block copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
  • various additives such as ultraviolet absorbers, lubricants, antistatic agents and flame retardants may be contained.
  • the method for dispersing the conductive particles in the binder is not particularly limited, and a conventionally known dispersion method can be used.
  • a method for dispersing the conductive particles in the binder after adding the conductive particles in the binder, a method of kneading and dispersing with a planetary mixer or the like, the conductive particles in water or an organic solvent And a homogenizer or the like, and then added to the binder and kneaded and dispersed by a planetary mixer or the like.
  • the conductive particles are added, and kneaded and dispersed by a planetary mixer or the like. Is mentioned.
  • the conductive material can be used as a conductive paste and a conductive film.
  • the conductive material is a conductive film
  • a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, and particularly preferably 70% by weight or more, preferably It is 99.99 weight% or less, More preferably, it is 99.9 weight% or less.
  • the content of the binder is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. % Or less, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
  • the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.
  • the adhesive according to the present invention includes the resin particles described above and a binder.
  • the resin particles are preferably used by being dispersed in a binder, and are preferably used as an adhesive by being dispersed in a binder.
  • the resin particles are preferably used as a spacer in the binder.
  • the adhesive may not contain conductive particles.
  • the adhesive is used to form an adhesive layer that adheres two connection target members. Further, the adhesive is used for controlling the gap of the adhesive layer with high accuracy, or for relaxing the stress of the adhesive layer.
  • the above binder is not particularly limited. Specific examples of the binder include binders used for the above-described conductive materials.
  • the adhesive preferably contains an epoxy resin as the binder.
  • the content of the binder in 100% by weight of the adhesive is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably It is 99.99 weight% or less, More preferably, it is 99.9 weight% or less.
  • the adhesive force of the adhesive layer can be further effectively increased, and the resin particles can more effectively exhibit the function as a spacer. can do.
  • the content of the resin particles in 100% by weight of the adhesive is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. Hereinafter, it is more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
  • the content of the resin particles is not less than the above lower limit and not more than the above upper limit, the resin particles can more effectively exhibit the function as a spacer.
  • connection structure can be obtained by connecting the connection target members using the conductive particles or using a conductive material containing the conductive particles and a binder.
  • connection structure includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connecting portion connecting the second connection target member.
  • the material of the connection part includes the resin particles described above. It is preferable that the material of the connection portion is the above-described conductive particles or the above-described conductive material. It is preferable that the connection portion is formed of the above-described conductive particles or a connection structure formed of the above-described conductive material.
  • connection part itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.
  • the conductive material used for obtaining the connection structure is preferably an anisotropic conductive material. It is preferable that the first electrode and the second electrode are electrically connected by the connecting portion.
  • FIG. 4 is a cross-sectional view showing an example of a connection structure using the conductive particles 1 shown in FIG.
  • connection structure 41 shown in FIG. 4 is a connection that connects the first connection target member 42, the second connection target member 43, and the first connection target member 42 and the second connection target member 43.
  • the connection part 44 is formed of a conductive material including the conductive particles 1 and a binder.
  • the conductive particles 1 are schematically shown for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 21 and 31 may be used.
  • the first connection target member 42 has a plurality of first electrodes 42a on the surface (upper surface).
  • the second connection target member 43 has a plurality of second electrodes 43a on the surface (lower surface).
  • the first electrode 42 a and the second electrode 43 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 42 and 43 are electrically connected by the conductive particles 1.
  • FIG. 5 is a cross-sectional view showing an example of a connection structure using the resin particles according to the present invention.
  • connection structure 51 shown in FIG. 5 is an adhesive that bonds the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53.
  • Layer 54 bonds the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53.
  • the adhesive layer 54 includes the resin particles 11 described above.
  • the resin particles 11 are not in contact with both the first and second connection target members 52 and 53.
  • the resin particles 11 are used as stress relaxation spacers.
  • the adhesive layer 54 includes gap control particles 61 and a thermosetting component 62.
  • the gap control particles 61 are in contact with both the first and second connection target members 52 and 53.
  • the gap control particles 61 may be conductive particles or non-conductive particles.
  • the gap control particles may be the resin particles described above.
  • the thermosetting component 62 includes a thermosetting compound and a thermosetting agent.
  • the thermosetting component 62 is a cured product of a thermosetting compound.
  • the thermosetting component 62 is formed by curing a thermosetting compound.
  • the first connection object member may have a first electrode on the surface.
  • the second connection target member may have a second electrode on the surface.
  • the manufacturing method of the connection structure is not particularly limited.
  • a method of manufacturing a connection structure a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc.
  • the pressure at the time of pressurization is about 9.8 ⁇ 10 4 Pa to 4.9 ⁇ 10 6 Pa.
  • the temperature during the heating is about 120 ° C. to 220 ° C.
  • the pressure at the time of pressurization for connecting the electrode of the flexible printed board, the electrode arranged on the resin film, and the electrode of the touch panel is about 9.8 ⁇ 10 4 Pa to 1.0 ⁇ 10 6 Pa.
  • connection target member examples include electronic components such as a semiconductor chip, a capacitor, and a diode, and electronic components such as a circuit board such as a printed board, a flexible printed board, a glass epoxy board, and a glass board.
  • the connection target member is preferably an electronic component.
  • At least one of the first connection target member and the second connection target member is preferably a semiconductor wafer or a semiconductor chip.
  • the connection structure is preferably a semiconductor device.
  • the conductive material is preferably a conductive material for connecting electronic components.
  • the conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in a paste-like state.
  • connection target member is preferably a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film.
  • the connection target member is preferably a flexible substrate, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film.
  • the flexible substrate is a flexible printed substrate or the like, the flexible substrate generally has electrodes on the surface.
  • the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a silver electrode, a SUS electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
  • the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
  • the trivalent metal element include Sn, Al, and Ga.
  • the resin particles can be suitably used as a spacer for a liquid crystal display element.
  • the liquid crystal display element according to the present invention includes a first liquid crystal display element member, a second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member. And a spacer disposed therebetween.
  • the spacer is the resin particle described above.
  • the liquid crystal display element has the first liquid crystal display element member and the second liquid crystal display element member in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other. You may provide the seal
  • the resin particles can also be used as a peripheral sealing agent for liquid crystal display elements.
  • the first liquid crystal display element member, the second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member face each other.
  • the liquid crystal display element includes a liquid crystal disposed between the first liquid crystal display element member and the second liquid crystal display element member inside the seal portion. In this liquid crystal display element, a liquid crystal dropping method is applied, and the seal portion is formed by thermosetting a sealing agent for a liquid crystal dropping method.
  • FIG. 6 is a cross-sectional view showing an example of a liquid crystal display element using the resin particles according to the present invention as a spacer for a liquid crystal display element.
  • a liquid crystal display element 81 illustrated in FIG. 6 includes a pair of transparent glass substrates 82.
  • the transparent glass substrate 82 has an insulating film (not shown) on the opposing surface. Examples of the material for the insulating film include SiO 2 .
  • a transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. Examples of the material of the transparent electrode 83 include ITO.
  • the transparent electrode 83 can be formed by patterning, for example, by photolithography.
  • An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. Examples of the material of the alignment film 84 include polyimide.
  • a liquid crystal 85 is sealed between the pair of transparent glass substrates 82.
  • a plurality of resin particles 11 are disposed between the pair of transparent glass substrates 82.
  • the resin particle 11 is used as a spacer for a liquid crystal display element.
  • the interval between the pair of transparent glass substrates 82 is regulated by the plurality of resin particles 11.
  • a sealing agent 86 is disposed between the edges of the pair of transparent glass substrates 82. Outflow of the liquid crystal 85 to the outside is prevented by the sealing agent 86.
  • the sealing agent 86 includes resin particles 11A that differ from the resin particles 11 only in particle diameter.
  • the arrangement density of spacers for liquid crystal display elements per 1 mm 2 is preferably 10 pieces / mm 2 or more, and preferably 1000 pieces / mm 2 or less.
  • the arrangement density is 10 pieces / mm 2 or more, the cell gap becomes even more uniform.
  • the arrangement density is 1000 / mm 2 or less, the contrast of the liquid crystal display element is further improved.
  • Example 1 Production of resin particles Polystyrene particles having an average particle diameter of 6.0 ⁇ m were prepared as seed particles. 5.0 parts by weight of the polystyrene particles, 900 parts by weight of ion-exchanged water, and 170 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol were mixed to prepare a mixed solution. After the above mixed solution was dispersed by ultrasonic waves, it was put into a separable flask and stirred uniformly.
  • cyclohexyl methacrylate is prepared as the first polymerizable compound 1 having one polymerizable functional group and having a cyclic organic group, and having a polymerizable functional group and having a cyclic organic group.
  • Isobornyl acrylate was prepared as 1 polymerizable compound 2.
  • divinylbenzene was prepared as a second polymerizable compound having two or more polymerizable functional groups and having a cyclic organic group.
  • the emulsion was further added to the mixed solution in the separable flask and stirred for 16 hours to absorb the monomer in the seed particles, thereby obtaining a suspension containing seed particles in which the monomer was swollen.
  • Thermosetting compound A Epoxy compound (“EP-3300P” manufactured by Nagase ChemteX Corporation)
  • Thermosetting compound B Epoxy compound (“EPICLON HP-4032D” manufactured by DIC)
  • Thermosetting compound C Epoxy compound (“Epogosei PT”, polytetramethylene glycol diglycidyl ether, manufactured by Yokkaichi Gosei Co., Ltd.)
  • a conductive material (anisotropic conductive paste) was produced as follows.
  • thermosetting compound A 10 parts by weight of thermosetting compound A, 10 parts by weight of thermosetting compound B, 15 parts by weight of thermosetting compound C, 5 parts by weight of thermosetting agent, and 20 parts by weight of filler were blended to obtain a blend. Furthermore, after adding the obtained electroconductive particle so that content in 100 weight% of compounds may be 10 weight%, it stirs at 2000 rpm for 5 minutes using a planetary stirrer, and conductive material (anisotropic) Conductive paste) was obtained.
  • connection structure As a first connection target member, a glass substrate having an aluminum electrode pattern with an L / S of 20 ⁇ m / 20 ⁇ m on the upper surface was prepared. As a second connection target member, a semiconductor chip having a gold electrode pattern (gold electrode thickness: 20 ⁇ m) with L / S of 20 ⁇ m / 20 ⁇ m on the lower surface was prepared.
  • the conductive material (anisotropic conductive paste) immediately after fabrication was applied to the upper surface of the glass substrate so as to have a thickness of 30 ⁇ m to form a conductive material (anisotropic conductive paste) layer.
  • the semiconductor chip was stacked on the upper surface of the conductive material (anisotropic conductive paste) layer so that the electrodes face each other.
  • a pressure heating head is placed on the upper surface of the semiconductor chip, and the conductive material (anisotropic conductive paste)
  • the layer was cured under the conditions of 170 ° C., 1.0 MPa, and 15 seconds to obtain a connection structure.
  • Example 2 When preparing resin particles, 9 parts by weight of polytetramethylene glycol diacrylate was changed to 91 parts by weight of methyl methacrylate, the amount of cyclohexyl methacrylate was changed from 15 parts by weight to 5 parts by weight, and isobornyl acrylate was changed from 75 parts by weight to 3 parts by weight. Except for the above change, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1.
  • Example 3 In the same manner as in Example 1, except that 9 parts by weight of polytetramethylene glycol diacrylate was changed to 9 parts by weight of 2-methacryloxyethyl acid phosphate when preparing the resin particles, the conductive particles and the conductive material were used. And the connection structure was obtained.
  • Example 4 Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 2 except that 5 parts by weight of cyclohexyl methacrylate was changed to 5 parts by weight of phenoxyethylene glycol methacrylate when producing the resin particles. .
  • Example 5 Conductive particles, conductive materials, and connection structures were obtained in the same manner as in Example 2 except that 5 parts by weight of cyclohexyl methacrylate was changed to 5 parts by weight of dicyclopentenyl acrylate when producing the resin particles. .
  • Example 6 The conductive particles, the conductive material, and the connection structure were prepared in the same manner as in Example 1 except that 1 part by weight of divinylbenzene was changed to 1 part by weight of tricyclodecane dimethanol diacrylate when the resin particles were produced. Obtained.
  • Comparative Example 4 Conductive particles, conductive materials, and connection structures were obtained in the same manner as in Comparative Example 1 except that 15 parts by weight of cyclohexyl methacrylate was changed to 15 parts by weight of phenoxyethylene glycol methacrylate when producing the resin particles. .
  • the resin particles used for measurement of the particle diameter were heated at 150 ° C. for 1000 hours.
  • the particle diameter of the resin particles after heating for 1000 hours was measured by the method described above. From the measurement results obtained, the ratio of the particle diameter of the resin particles after heating to the particle diameter of the resin particles before heating (the particle diameter of the resin particles after heating / the particle diameter of the resin particles before heating) was calculated.
  • the resin particles used for the measurement of 30% K value were heated at 150 ° C. for 1000 hours.
  • the 30% K value of the resin particles after heating for 1000 hours was measured by the method described above. From the measurement results obtained, the ratio of the 30% K value after heating to the 30% K value before heating (30% K value after heating / 30% K value before heating) was calculated.
  • the obtained electroconductive particle was heated at 150 degreeC for 1000 hours. Fifty plating states of the conductive particles after heating were observed with a scanning electron microscope. The presence or absence of plating unevenness such as plating cracking or peeling off was evaluated. The plating state was determined according to the following criteria.
  • connection strength The connection strength at 260 ° C. of the obtained connection structure was measured using a mount strength measuring device. Connection strength was determined according to the following criteria.
  • Shear strength is 150 N / cm 2 or more
  • Shear strength is 100 N / cm 2 or more and less than 150 N / cm 2
  • Shear strength is less than 100 N / cm 2
  • Springback With a scanning electron microscope, it was observed whether or not springback occurred at the connection portion of the obtained connection structure. Springback was determined according to the following criteria.
  • connection reliability The obtained connection structure was heated from ⁇ 65 ° C. to 150 ° C. and cooled to ⁇ 65 ° C., and a cooling cycle test was performed for 1000 cycles. With an ultrasonic flaw detector (SAT), the presence or absence of floating or peeling at the connecting portion was observed.
  • the thermal cycle characteristics (connection reliability) were determined according to the following criteria.
  • connection reliability [Criteria for cooling cycle characteristics (connection reliability)] ⁇ : No floating or peeling at the connection part ⁇ : There is floating or peeling at the connection part
  • An SiO 2 film was deposited on one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm) by a CVD method, and then an ITO film was formed on the entire surface of the SiO 2 film by sputtering.
  • a polyimide alignment film composition (SE3510, manufactured by Nissan Chemical Industries, Ltd.) was applied to the obtained glass substrate with an ITO film by spin coating, and baked at 280 ° C. for 90 minutes to form a polyimide alignment film. After the alignment film was rubbed, wet alignment was performed on the alignment film side of one substrate so that the number of spacers for liquid crystal display elements was 100 per 1 mm 2 .
  • this substrate and the substrate on which the spacers were spread were placed opposite to each other so that the rubbing direction was 90 °, and both were bonded together. Then, it processed at 160 degreeC for 90 minute (s), the sealing agent was hardened, and the empty cell (screen which does not contain a liquid crystal) was obtained. An STN type liquid crystal containing a chiral agent (made by DIC) was injected into the obtained empty cell, and then the injection port was closed with a sealant, followed by heat treatment at 120 ° C. for 30 minutes to produce an STN type liquid crystal display element. Obtained.
  • the distance between the substrates was well regulated by the spacers (resin particles) for liquid crystal display elements of Examples 1 to 6. Moreover, the liquid crystal display element showed favorable display quality. Even when the resin particles of Examples 1 to 6 were used as the spacer for the liquid crystal display element as the peripheral sealant of the liquid crystal display element, the display quality of the obtained liquid crystal display element was good.

Abstract

Provided are resin particles which are capable of effectively suppressing the occurrence of spring back, and which are also capable of effectively suppressing the occurrence of lifting or separation. Resin particles according to the present invention are composed of a polymer of a first polymerizable compound that has one polymerizable functional group and a cyclic organic group and a second polymerizable compound that has two or more polymerizable functional groups and a cyclic organic group. The weight ratio of the content of the structural unit derived from the first polymerizable compound to the content of the structural unit derived from the second polymerizable compound is 7 or more. If the resin particles are heated at 150°C for 1,000 hours, the ratio of the particle diameters of the resin particles after heating to the particle diameters of the resin particles before heating is 0.9 or less.

Description

樹脂粒子、導電性粒子、導電材料、接着剤、接続構造体及び液晶表示素子Resin particles, conductive particles, conductive materials, adhesives, connection structures, and liquid crystal display elements
　本発明は、樹脂により形成された樹脂粒子に関する。また、本発明は、上記樹脂粒子を用いた導電性粒子、導電材料、接着剤、接続構造体及び液晶表示素子に関する。 The present invention relates to resin particles formed of a resin. The present invention also relates to conductive particles, conductive materials, adhesives, connection structures and liquid crystal display elements using the resin particles.
　異方性導電ペースト及び異方性導電フィルム等の異方性導電材料が広く知られている。上記異方性導電材料では、バインダー中に導電性粒子が分散されている。 Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder.
　上記異方性導電材料は、フレキシブルプリント基板（ＦＰＣ）、ガラス基板、ガラスエポキシ基板及び半導体チップ等の様々な接続対象部材の電極間を電気的に接続し、接続構造体を得るために用いられている。また、上記導電性粒子として、樹脂粒子と、該樹脂粒子の表面上に配置された導電部とを有する導電性粒子が用いられることがある。 The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing. Moreover, as the conductive particles, conductive particles having resin particles and conductive portions arranged on the surface of the resin particles may be used.
　また、液晶表示素子は、２枚のガラス基板間に液晶が配置されて構成されている。該液晶表示素子では、２枚のガラス基板の間隔（ギャップ）を均一かつ一定に保つために、ギャップ制御材としてスペーサが用いられている。該スペーサとして、樹脂粒子が一般に用いられている。 Further, the liquid crystal display element is configured by arranging liquid crystal between two glass substrates. In the liquid crystal display element, a spacer is used as a gap control material in order to keep the distance (gap) between two glass substrates uniform and constant. As the spacer, resin particles are generally used.
　上記導電性粒子の一例として、下記の特許文献１では、重合体粒子と、該重合体粒子の表面を被覆している導電層とを有する導電性粒子が開示されている。上記重合体粒子は、２官能の（メタ）アクリレートモノマー、３官能の（メタ）アクリレートモノマー、及び４官能の（メタ）アクリレートモノマーの内の少なくとも１種の多官能（メタ）アクリレートと、単官能の（メタ）アクリレートモノマーとを含む共重合成分を共重合させることにより得られる。上記２官能の（メタ）アクリレートモノマーは、１，１０－デカンジオールジ（メタ）アクリレートである。上記多官能（メタ）アクリレートが上記２官能の（メタ）アクリレートモノマーを含む場合には、上記共重合成分は、上記２官能の（メタ）アクリレートモノマー１００重量部に対して、上記単管能の（メタ）アクリレートモノマーを１０重量部～４００重量部の範囲で含有する。上記多官能（メタ）アクリレートが上記４官能の（メタ）アクリレートモノマーを含む場合には、上記共重合成分は、上記４官能の（メタ）アクリレートモノマーと上記単管能の（メタ）アクリレートモノマーとの合計１００重量％中、上記単管能の（メタ）アクリレートモノマーを８０重量％以下で含有する。上記重合体粒子の圧縮変形回復率は、７０％以上である。上記重合体粒子の体積膨張率は、１．３以下である。 As an example of the conductive particles, the following Patent Document 1 discloses conductive particles having polymer particles and a conductive layer covering the surface of the polymer particles. The polymer particle is composed of at least one polyfunctional (meth) acrylate selected from a bifunctional (meth) acrylate monomer, a trifunctional (meth) acrylate monomer, and a tetrafunctional (meth) acrylate monomer, and a monofunctional It is obtained by copolymerizing a copolymerization component containing the (meth) acrylate monomer. The bifunctional (meth) acrylate monomer is 1,10-decandiol di (meth) acrylate. In the case where the polyfunctional (meth) acrylate includes the bifunctional (meth) acrylate monomer, the copolymerization component has the above-mentioned single-tube ability with respect to 100 parts by weight of the bifunctional (meth) acrylate monomer. A (meth) acrylate monomer is contained in the range of 10 to 400 parts by weight. When the polyfunctional (meth) acrylate includes the tetrafunctional (meth) acrylate monomer, the copolymer component includes the tetrafunctional (meth) acrylate monomer and the monofunctional (meth) acrylate monomer. In the total 100% by weight, the above-mentioned single-capacity (meth) acrylate monomer is contained at 80% by weight or less. The compression deformation recovery rate of the polymer particles is 70% or more. The volume expansion coefficient of the polymer particles is 1.3 or less.
　また、上記導電性粒子又は上記スペーサに用いられる樹脂粒子の一例として、下記の特許文献２では、架橋（メタ）アクリル酸エステル系樹脂から構成されている高復元性樹脂粒子が開示されている。上記高復元性樹脂粒子の平均粒子径は、１μｍ～１００μｍである。上記高復元性樹脂粒子の復元率は、２２％以上である。上記高復元性樹脂粒子の３０％圧縮強度は、１．５ｋｇｆ／ｍｍ２～５．０ｋｇｆ／ｍｍ２である。 In addition, as an example of the resin particles used for the conductive particles or the spacers, the following Patent Document 2 discloses highly resilient resin particles composed of a crosslinked (meth) acrylic ester resin. The average particle size of the highly restorable resin particles is 1 μm to 100 μm. The restoration rate of the highly restoring resin particles is 22% or more. 30% compressive strength of the high resilience resin particles is 1.5kgf / mm 2 ~ 5.0kgf / mm 2.
ＷＯ２０１０／０１３６６８Ａ１WO2010 / 013668A1 ＷＯ２０１６／０３９３５７Ａ１WO2016 / 039357A1
　従来の樹脂粒子を導電性粒子やスペーサとして用いる場合には、圧縮された樹脂粒子が元の形状に戻ろうとする作用が働いて、スプリングバックと呼ばれる現象が生じることがある。導電性粒子として用いられた樹脂粒子にスプリングバックが発生すると、導電性粒子と電極との接触面積が低下して、導通信頼性が低下することがある。また、スペーサとして用いられた樹脂粒子にスプリングバックが発生すると、スペーサと液晶表示素子用部材等とが十分に接触せず、ギャップ制御効果が十分に得られないことがある。 When conventional resin particles are used as conductive particles or spacers, the action of the compressed resin particles returning to their original shape may occur, and a phenomenon called spring back may occur. When spring back occurs in the resin particles used as the conductive particles, the contact area between the conductive particles and the electrode may decrease, and the conduction reliability may decrease. In addition, when spring back occurs in the resin particles used as the spacer, the spacer and the liquid crystal display element member or the like are not sufficiently in contact, and the gap control effect may not be sufficiently obtained.
　また、導電性粒子とバインダーとを含む導電材料や、スペーサとバインダーとを含む接着剤は、使用時に加熱環境に曝されることがあり、バインダーが硬化収縮することがある。従来の樹脂粒子は、加熱時に十分に収縮せず、バインダーの硬化収縮に追随することができないことがある。結果として、導電材料と電極との間、又は、接着剤と液晶表示素子用部材等との間において、浮き又は剥離が発生することがある。 Also, a conductive material containing conductive particles and a binder and an adhesive containing a spacer and a binder may be exposed to a heating environment during use, and the binder may be cured and shrunk. Conventional resin particles may not shrink sufficiently upon heating and may not be able to follow the curing shrinkage of the binder. As a result, floating or peeling may occur between the conductive material and the electrode or between the adhesive and the liquid crystal display element member or the like.
　本発明の目的は、スプリングバックの発生を効果的に抑制することができ、かつ、浮き又は剥離の発生を効果的に抑制することができる樹脂粒子を提供することである。また、本発明の目的は、上記樹脂粒子を用いた導電性粒子、導電材料、接着剤、接続構造体及び液晶表示素子を提供することである。 An object of the present invention is to provide resin particles that can effectively suppress the occurrence of springback and can effectively suppress the occurrence of floating or peeling. Another object of the present invention is to provide conductive particles, conductive materials, adhesives, connection structures and liquid crystal display elements using the resin particles.
　本発明の広い局面によれば、重合性官能基を１個有し、かつ環状有機基を有する第１の重合性化合物と、重合性官能基を２個以上有し、かつ環状有機基を有する第２の重合性化合物との重合体であり、前記第１の重合性化合物に由来する構造の含有量の前記第２の重合性化合物に由来する構造の含有量に対する重量比が、７以上であり、樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の粒子径の加熱前の樹脂粒子の粒子径に対する比が、０．９以下である、樹脂粒子が提供される。 According to a wide aspect of the present invention, a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, two or more polymerizable functional groups, and having a cyclic organic group The polymer is a polymer with a second polymerizable compound, and the weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more. There is provided a resin particle in which, when the resin particle is heated at 150 ° C. for 1000 hours, the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating is 0.9 or less.
　本発明に係る樹脂粒子のある特定の局面では、６０％圧縮変形させた際の圧縮回復率が、１０％以下である。 In a specific aspect of the resin particles according to the present invention, the compression recovery rate when compressed and deformed by 60% is 10% or less.
　本発明に係る樹脂粒子のある特定の局面では、１０％Ｋ値が、３０００Ｎ／ｍｍ２以下である。 In a specific aspect of the resin particle according to the present invention, the 10% K value is 3000 N / mm 2 or less.
　本発明に係る樹脂粒子のある特定の局面では、３０％Ｋ値が、１５００Ｎ／ｍｍ２以下である。 In a specific aspect of the resin particle according to the present invention, the 30% K value is 1500 N / mm 2 or less.
　本発明に係る樹脂粒子のある特定の局面では、樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の３０％Ｋ値の加熱前の樹脂粒子の３０％Ｋ値に対する比が、０．８以上１．５以下である。 In a specific aspect of the resin particle according to the present invention, when the resin particle is heated at 150 ° C. for 1000 hours, the ratio of the 30% K value of the heated resin particle to the 30% K value of the resin particle before heating is 0.8 to 1.5.
　本発明に係る樹脂粒子のある特定の局面では、前記第１の重合性化合物における環状有機基と前記第２の重合性化合物における環状有機基とがそれぞれ、炭化水素基である。 In a specific aspect of the resin particle according to the present invention, the cyclic organic group in the first polymerizable compound and the cyclic organic group in the second polymerizable compound are each a hydrocarbon group.
　本発明に係る樹脂粒子のある特定の局面では、前記第１の重合性化合物における環状有機基が、フェニレン基、シクロヘキシル基又はイソボルニル基である。 In a specific aspect of the resin particle according to the present invention, the cyclic organic group in the first polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group.
　本発明に係る樹脂粒子のある特定の局面では、前記第２の重合性化合物における環状有機基が、フェニレン基、シクロヘキシル基又はイソボルニル基である。 In a specific aspect of the resin particle according to the present invention, the cyclic organic group in the second polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group.
　本発明に係る樹脂粒子のある特定の局面では、前記樹脂粒子は、アシッドホスフェート化合物を含む。 In a specific aspect of the resin particle according to the present invention, the resin particle contains an acid phosphate compound.
　本発明に係る樹脂粒子のある特定の局面では、前記樹脂粒子は、スペーサとして用いられるか、又は、表面上に導電部が形成され、前記導電部を有する導電性粒子を得るために用いられる。 In a specific aspect of the resin particle according to the present invention, the resin particle is used as a spacer, or a conductive part is formed on the surface and used to obtain conductive particles having the conductive part.
　本発明の広い局面によれば、上述した樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備える、導電性粒子が提供される。 According to a wide aspect of the present invention, there is provided a conductive particle comprising the resin particle described above and a conductive part disposed on the surface of the resin particle.
　本発明の広い局面によれば、導電性粒子と、バインダーとを含み、前記導電性粒子が、上述した樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備える、導電材料が提供される。 According to a wide aspect of the present invention, there is provided a conductive material including conductive particles and a binder, wherein the conductive particles include the resin particles described above and a conductive portion disposed on a surface of the resin particles. Provided.
　本発明の広い局面によれば、上述した樹脂粒子と、バインダーとを含む、接着剤が提供される。 According to a wide aspect of the present invention, there is provided an adhesive containing the above-described resin particles and a binder.
　本発明の広い局面によれば、第１の電極を表面に有する第１の接続対象部材と、第２の電極を表面に有する第２の接続対象部材と、前記第１の接続対象部材と、前記第２の接続対象部材とを接続している接続部とを備え、前記接続部の材料が、上述した樹脂粒子を含み、前記第１の電極と前記第２の電極とが、前記接続部により電気的に接続されている、接続構造体が提供される。 According to a wide aspect of the present invention, a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connecting portion connecting the second connection target member, wherein the material of the connecting portion includes the resin particles described above, and the first electrode and the second electrode are the connecting portion. To provide a connection structure that is electrically connected.
　本発明の広い局面によれば、第１の液晶表示素子用部材と、第２の液晶表示素子用部材と、前記第１の液晶表示素子用部材と前記第２の液晶表示素子用部材との間に配置されたスペーサとを備え、前記スペーサが、上述した樹脂粒子である、液晶表示素子が提供される。 According to a wide aspect of the present invention, the first liquid crystal display element member, the second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member There is provided a liquid crystal display element including a spacer disposed between the spacers, the spacer being the resin particles described above.
　本発明に係る樹脂粒子は、重合性官能基を１個有し、かつ環状有機基を有する第１の重合性化合物と、重合性官能基を２個以上有し、かつ環状有機基を有する第２の重合性化合物との重合体である。本発明に係る樹脂粒子では、上記第１の重合性化合物に由来する構造の含有量の上記第２の重合性化合物に由来する構造の含有量に対する重量比が、７以上である。本発明に係る樹脂粒子では、樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の粒子径の加熱前の樹脂粒子の粒子径に対する比が、０．９以下である。本発明に係る樹脂粒子では、上記の構成が備えられているので、スプリングバックの発生を効果的に抑制することができ、かつ、浮き又は剥離の発生を効果的に抑制することができる。 The resin particles according to the present invention include a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and two or more polymerizable functional groups and having a cyclic organic group. 2 is a polymer with a polymerizable compound. In the resin particles according to the present invention, the weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more. In the resin particle according to the present invention, when the resin particle is heated at 150 ° C. for 1000 hours, the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating is 0.9 or less. Since the resin particles according to the present invention have the above-described configuration, the occurrence of springback can be effectively suppressed, and the occurrence of floating or peeling can be effectively suppressed.
図１は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. 図２は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention. 図３は、本発明の第３の実施形態に係る導電性粒子を示す断面図である。FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention. 図４は、本発明の第１の実施形態に係る導電性粒子を用いた接続構造体の一例を示す断面図である。FIG. 4 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention. 図５は、本発明に係る樹脂粒子を用いた接続構造体の一例を示す断面図である。FIG. 5 is a cross-sectional view showing an example of a connection structure using the resin particles according to the present invention. 図６は、本発明に係る樹脂粒子を液晶表示素子用スペーサとして用いた液晶表示素子の一例を示す断面図である。FIG. 6 is a cross-sectional view showing an example of a liquid crystal display element using the resin particles according to the present invention as a spacer for a liquid crystal display element.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　（樹脂粒子）
　本発明に係る樹脂粒子は、重合性官能基を１個有し、かつ環状有機基を有する第１の重合性化合物と、重合性官能基を２個以上有し、かつ環状有機基を有する第２の重合性化合物との重合体である。本発明に係る樹脂粒子では、上記第１の重合性化合物に由来する構造の含有量（ＷＭ）の、上記第２の重合性化合物に由来する構造の含有量（ＷＤ）に対する重量比（ＷＭ／ＷＤ）は、７以上である。本発明に係る樹脂粒子では、樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の粒子径の加熱前の樹脂粒子の粒子径に対する比（加熱後の樹脂粒子の粒子径／加熱前の樹脂粒子の粒子径）は、０．９以下である。 (Resin particles)
The resin particles according to the present invention include a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and two or more polymerizable functional groups and having a cyclic organic group. 2 is a polymer with a polymerizable compound. In the resin particles according to the present invention, the weight ratio (WM / W) of the content (WM) derived from the first polymerizable compound to the content (WD) derived from the second polymerizable compound. WD) is 7 or more. In the resin particle according to the present invention, when the resin particle is heated at 150 ° C. for 1000 hours, the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating (the particle diameter of the resin particle after heating / The particle diameter of the resin particles before heating) is 0.9 or less.
　本発明では、上記の構成が備えられているので、スプリングバックの発生を効果的に抑制することができ、かつ、浮き又は剥離の発生を効果的に抑制することができる。 In the present invention, since the above configuration is provided, the occurrence of springback can be effectively suppressed, and the occurrence of floating or peeling can be effectively suppressed.
　本発明に係る樹脂粒子では、上記の構成が備えられているので、圧縮回復率が比較的低く、圧縮された樹脂粒子が元の形状に戻ろうとする作用が比較的働き難く、スプリングバックが発生し難い。例えば、本発明に係る樹脂粒子を導電性粒子として用いた場合には、導電性粒子と電極との接触面積の低下を効果的に防止することができ、電極間の導通信頼性を効果的に高めることができる。また、本発明に係る樹脂粒子をスペーサとして用いた場合には、スペーサを液晶表示素子用部材等に十分に接触させることができ、ギャップをより一層高精度に制御することができる。 Since the resin particles according to the present invention have the above-described configuration, the compression recovery rate is relatively low, the action of the compressed resin particles trying to return to the original shape is relatively difficult, and a springback occurs. It is hard to do. For example, when the resin particles according to the present invention are used as conductive particles, a decrease in the contact area between the conductive particles and the electrodes can be effectively prevented, and the conduction reliability between the electrodes can be effectively reduced. Can be increased. When the resin particles according to the present invention are used as a spacer, the spacer can be sufficiently brought into contact with a liquid crystal display element member and the like, and the gap can be controlled with higher accuracy.
　また、導電性粒子とバインダーとを含む導電材料や、スペーサとバインダーとを含む接着剤は、使用時に加熱環境に曝されることがあり、加熱によりバインダーが硬化収縮することがある。本発明に係る樹脂粒子では、上記の構成が備えられているので、樹脂粒子が加熱により比較的容易に収縮する。加熱後の樹脂粒子の粒子径は、加熱前の樹脂粒子の粒子径よりも適度に小さくなるので、樹脂粒子がバインダーの硬化収縮にも追随することができる。結果として、導電材料と電極との間、又は、接着剤と液晶表示素子用部材等との間において、浮き又は剥離の発生を効果的に抑制することができる。 Also, a conductive material containing conductive particles and a binder and an adhesive containing a spacer and a binder may be exposed to a heating environment during use, and the binder may be cured and shrunk by heating. Since the resin particles according to the present invention have the above-described configuration, the resin particles shrink relatively easily by heating. Since the particle diameter of the resin particles after heating is appropriately smaller than the particle diameter of the resin particles before heating, the resin particles can follow the curing shrinkage of the binder. As a result, it is possible to effectively suppress the occurrence of floating or peeling between the conductive material and the electrode, or between the adhesive and the liquid crystal display element member.
　本発明に係る樹脂粒子では、上記第１の重合性化合物に由来する構造の含有量（ＷＭ）の、上記第２の重合性化合物に由来する構造の含有量（ＷＤ）に対する重量比（ＷＭ／ＷＤ）は、７以上である。スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記重量比（ＷＭ／ＷＤ）は、好ましくは９以上、より好ましくは１３以上であり、好ましくは２０以下、より好ましくは１７以下である。 In the resin particles according to the present invention, the weight ratio (WM / W) of the content (WM) derived from the first polymerizable compound to the content (WD) derived from the second polymerizable compound. WD) is 7 or more. From the viewpoint of more effectively suppressing the occurrence of springback and further effectively suppressing the occurrence of floating or peeling, the weight ratio (WM / WD) is preferably 9 or more, more preferably It is 13 or more, preferably 20 or less, more preferably 17 or less.
　上記第１の重合性化合物に由来する構造の含有量（ＷＭ）及び上記第２の重合性化合物に由来する構造の含有量（ＷＤ）を求める方法としては、以下の方法が挙げられる。重合体を得る際に用いた第１，第２の重合性化合物の配合量及び重合後の第１，第２の重合性化合物の残存量から、重合した第１，第２の重合性化合物の量を求め、重合した第１，第２の重合性化合物の量から算出する。 The following methods may be mentioned as methods for determining the content (WM) derived from the first polymerizable compound and the content (WD) derived from the second polymerizable compound. From the blended amount of the first and second polymerizable compounds used in obtaining the polymer and the remaining amount of the first and second polymerizable compounds after polymerization, the polymerized first and second polymerizable compounds The amount is determined and calculated from the amount of the first and second polymerizable compounds polymerized.
　また、樹脂粒子から上記第１の重合性化合物に由来する構造の含有量（ＷＭ）及び上記第２の重合性化合物に由来する構造の含有量（ＷＤ）を求める方法としては、以下の方法が挙げられる。重合体を得る際に用いた第１，第２の重合性化合物のそれぞれの樹脂粒子における官能基の量や、重合体を得る際に用いた第１，第２の重合性化合物のそれぞれの樹脂粒子における官能基が反応した基の量から算出する。 In addition, as a method for obtaining the content (WM) of the structure derived from the first polymerizable compound and the content (WD) of the structure derived from the second polymerizable compound from the resin particles, the following methods are used. Can be mentioned. The amount of functional groups in the respective resin particles of the first and second polymerizable compounds used when obtaining the polymer, and the respective resins of the first and second polymerizable compounds used when obtaining the polymer It calculates from the quantity of the group which the functional group in particle | grains reacted.
　本発明に係る樹脂粒子では、樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の粒子径の加熱前の樹脂粒子の粒子径に対する比（加熱後の樹脂粒子の粒子径／加熱前の樹脂粒子の粒子径）は、０．９以下である。浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記比（加熱後の樹脂粒子の粒子径／加熱前の樹脂粒子の粒子径）は、好ましくは０．４以上、より好ましくは０．６以上であり、好ましくは０．８５以下、より好ましくは０．８以下である。 In the resin particle according to the present invention, when the resin particle is heated at 150 ° C. for 1000 hours, the ratio of the particle diameter of the resin particle after heating to the particle diameter of the resin particle before heating (particle diameter of resin particle after heating / The particle diameter of the resin particles before heating) is 0.9 or less. From the viewpoint of more effectively suppressing the occurrence of floating or peeling, the above ratio (particle diameter of resin particles after heating / particle diameter of resin particles before heating) is preferably 0.4 or more, more preferably It is 0.6 or more, preferably 0.85 or less, more preferably 0.8 or less.
　上記樹脂粒子の粒子径（上記加熱前の樹脂粒子の粒子径）は、用途に応じて適宜設定することができる。上記樹脂粒子の粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上であり、好ましくは５００μｍ以下、より好ましくは３００μｍ以下、より一層好ましくは１５０μｍ以下、さらに好ましくは１００μｍ以下、特に好ましくは５０μｍ以下である。上記樹脂粒子の粒子径が、上記下限以上及び上記上限以下であると、スプリングバックの発生をより一層効果的に抑制することができ、かつ、浮き又は剥離の発生をより一層効果的に抑制することができる。上記樹脂粒子の粒子径が、０．５μｍ以上５００μｍ以下であると、上記樹脂粒子を導電性粒子の用途に好適に用いることができる。上記樹脂粒子の粒子径が、０．５μｍ以上５００μｍ以下であると、上記樹脂粒子をスペーサの用途に好適に用いることができる。 The particle size of the resin particles (the particle size of the resin particles before heating) can be appropriately set depending on the application. The particle diameter of the resin particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 300 μm or less, still more preferably 150 μm or less, still more preferably 100 μm or less, particularly preferably. 50 μm or less. When the particle diameter of the resin particles is not less than the above lower limit and not more than the above upper limit, the occurrence of springback can be more effectively suppressed, and the occurrence of floating or peeling can be further effectively suppressed. be able to. When the particle size of the resin particles is 0.5 μm or more and 500 μm or less, the resin particles can be suitably used for conductive particles. When the particle diameter of the resin particles is 0.5 μm or more and 500 μm or less, the resin particles can be suitably used for spacer applications.
　上記樹脂粒子の粒子径（加熱前の樹脂粒子の粒子径及び加熱後の樹脂粒子の粒子径）は、樹脂粒子が真球状である場合には、直径を示し、樹脂粒子が真球状ではない場合には、最大径を示す。 The particle diameter of the resin particles (the particle diameter of the resin particles before heating and the particle diameter of the resin particles after heating) indicates the diameter when the resin particles are spherical, and the resin particles are not spherical. Shows the maximum diameter.
　上記樹脂粒子の粒子径（加熱前の樹脂粒子の粒子径及び加熱後の樹脂粒子の粒子径）は、平均粒子径であることが好ましく、数平均粒子径であることがより好ましい。上記樹脂粒子の粒子径は、粒度分布測定装置等を用いて求められる。例えば、レーザー散乱光、電気抵抗値変化、撮像後の画像解析等の原理を用いた粒度分布測定装置を用いることができる。具体的には、樹脂粒子の粒子径の測定方法としては、例えば、粒度分布測定装置（ベックマンコールター社製「Ｍｕｌｔｉｓｉｚｅｒ４」）を用いて、約１０００００個の樹脂粒子の粒子径を測定し、平均値を算出する方法等が挙げられる。樹脂粒子の粒子径は、任意の樹脂粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することにより求めることが好ましい。導電性粒子において、上記樹脂粒子の粒子径を測定する場合には、例えば、以下のようにして測定できる。 The particle size of the resin particles (the particle size of the resin particles before heating and the particle size of the resin particles after heating) is preferably an average particle size, and more preferably a number average particle size. The particle diameter of the resin particles is determined using a particle size distribution measuring device or the like. For example, a particle size distribution measuring apparatus using principles such as laser scattered light, electrical resistance value change, and image analysis after imaging can be used. Specifically, as a method for measuring the particle size of the resin particles, for example, using a particle size distribution measuring device (“Multizer 4” manufactured by Beckman Coulter, Inc.), the particle size of about 100,000 resin particles is measured, and the average value is measured. The method etc. of calculating are mentioned. The particle diameter of the resin particles is preferably obtained by observing 50 arbitrary resin particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the particle diameter of the resin particles in the conductive particles, for example, it can be measured as follows.
　導電性粒子の含有量が３０重量％となるように、Ｋｕｌｚｅｒ社製「テクノビット４０００」に添加し、分散させて、導電性粒子検査用埋め込み樹脂を作製する。検査用埋め込み樹脂中に分散した導電性粒子の中心付近を通るようにイオンミリング装置（日立ハイテクノロジーズ社製「ＩＭ４０００」）を用いて、導電性粒子の断面を切り出す。そして、電界放射型走査型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて、画像倍率を２５０００倍に設定し、５０個の導電性粒子を無作為に選択し、各導電性粒子の樹脂粒子を観察する。各導電性粒子における樹脂粒子の粒子径を計測し、それらを算術平均して樹脂粒子の粒子径とする。 An embedded resin for inspecting conductive particles is prepared by adding to and dispersing in “Technobit 4000” manufactured by Kulzer so that the content of the conductive particles is 30% by weight. A cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the conductive particles dispersed in the embedding resin for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification is set to 25000 times, 50 conductive particles are randomly selected, and the resin particles of each conductive particle are observed. . The particle diameter of the resin particle in each conductive particle is measured, and arithmetically averaged to obtain the particle diameter of the resin particle.
　スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記樹脂粒子の粒子径の変動係数（ＣＶ値）は、好ましくは０．５％以上、より好ましくは１％以上であり、好ましくは１０％以下、より好ましくは７％以下である。上記樹脂粒子の粒子径の変動係数が、上記下限以上及び上記上限以下であると、上記樹脂粒子をスペーサ及び導電性粒子の用途に好適に用いることができる。但し、上記樹脂粒子の粒子径の変動係数は、０．５％未満であってもよい。 From the viewpoint of more effectively suppressing the occurrence of springback and more effectively suppressing the occurrence of floating or peeling, the coefficient of variation (CV value) of the particle diameter of the resin particles is preferably 0. 0.5% or more, more preferably 1% or more, preferably 10% or less, more preferably 7% or less. When the coefficient of variation of the particle diameter of the resin particles is not less than the above lower limit and not more than the above upper limit, the resin particles can be suitably used for spacers and conductive particles. However, the coefficient of variation of the particle diameter of the resin particles may be less than 0.5%.
　上記変動係数（ＣＶ値）は、以下のようにして測定できる。 The coefficient of variation (CV value) can be measured as follows.
　ＣＶ値（％）＝（ρ／Ｄｎ）×１００
　ρ：樹脂粒子の粒子径の標準偏差
　Ｄｎ：樹脂粒子の粒子径の平均値 CV value (%) = (ρ / Dn) × 100
ρ: standard deviation of particle diameter of resin particles Dn: average value of particle diameter of resin particles
　上記樹脂粒子の形状は特に限定されない。上記樹脂粒子の形状は、球状であってもよく、扁平状等の球形状以外の形状であってもよい。 The shape of the resin particles is not particularly limited. The resin particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
　樹脂粒子の１０％Ｋ値は、好ましくは１０００Ｎ／ｍｍ２以上、より好ましくは１５００Ｎ／ｍｍ２以上であり、好ましくは３０００Ｎ／ｍｍ２以下、より好ましくは２７５０Ｎ／ｍｍ２以下、さらに好ましくは２５００Ｎ／ｍｍ２以下である。上記樹脂粒子の１０％Ｋ値が、上記下限以上及び上記上限以下であると、スプリングバックの発生をより一層効果的に抑制することができ、かつ、浮き又は剥離の発生をより一層効果的に抑制することができる。 10% K value of the resin particles is preferably 1000 N / mm 2 or more, more preferably 1500 N / mm 2 or more, preferably 3000N / mm 2 or less, more preferably 2750N / mm 2 or less, more preferably 2500N / mm 2 or less. When the 10% K value of the resin particles is not less than the above lower limit and not more than the above upper limit, the occurrence of spring back can be more effectively suppressed, and the occurrence of floating or peeling can be more effectively achieved. Can be suppressed.
　樹脂粒子の３０％Ｋ値は、好ましくは３００Ｎ／ｍｍ２以上、より好ましくは５００Ｎ／ｍｍ２以上であり、好ましくは１５００Ｎ／ｍｍ２以下、より好ましくは１２００Ｎ／ｍｍ２以下、さらに好ましくは１０００Ｎ／ｍｍ２以下である。上記樹脂粒子の３０％Ｋ値が、上記下限以上及び上記上限以下であると、スプリングバックの発生をより一層効果的に抑制することができ、かつ、浮き又は剥離の発生をより一層効果的に抑制することができる。 30% K value of the resin particles is preferably 300N / mm 2 or more, more preferably 500 N / mm 2 or more, preferably 1500 N / mm 2 or less, more preferably 1200 N / mm 2 or less, more preferably 1000 N / mm 2 or less. When the 30% K value of the resin particles is not less than the above lower limit and not more than the above upper limit, the occurrence of spring back can be more effectively suppressed, and the occurrence of floating or peeling can be more effectively achieved. Can be suppressed.
　樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の３０％Ｋ値の加熱前の樹脂粒子の３０％Ｋ値に対する比（加熱後の樹脂粒子の３０％Ｋ値／加熱前の樹脂粒子の３０％Ｋ値）は、好ましくは０．８以上、より好ましくは１．１５以上、さらに好ましくは１．２以上である。樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の３０％Ｋ値の加熱前の樹脂粒子の３０％Ｋ値に対する比（加熱後の樹脂粒子の３０％Ｋ値／加熱前の樹脂粒子の３０％Ｋ値）は、好ましくは１．５以下、より好ましくは１．４５以下、さらに好ましくは１．４以下である。上記比（加熱後の樹脂粒子の３０％Ｋ値／加熱前の樹脂粒子の３０％Ｋ値）が、上記下限以上及び上記上限以下であると、スプリングバックの発生をより一層効果的に抑制することができ、かつ、浮き又は剥離の発生をより一層効果的に抑制することができる。 When the resin particles are heated at 150 ° C. for 1000 hours, the ratio of the 30% K value of the resin particles after heating to the 30% K value of the resin particles before heating (30% K value of the resin particles after heating / before heating) The 30% K value of the resin particles is preferably 0.8 or more, more preferably 1.15 or more, and still more preferably 1.2 or more. When the resin particles are heated at 150 ° C. for 1000 hours, the ratio of the 30% K value of the resin particles after heating to the 30% K value of the resin particles before heating (30% K value of the resin particles after heating / before heating) The 30% K value of the resin particles is preferably 1.5 or less, more preferably 1.45 or less, and still more preferably 1.4 or less. When the ratio (30% K value of the heated resin particles / 30% K value of the resin particles before heating) is not less than the above lower limit and not more than the above upper limit, the occurrence of springback is more effectively suppressed. And the occurrence of floating or peeling can be more effectively suppressed.
　上記樹脂粒子の１０％Ｋ値及び３０％Ｋ値（樹脂粒子を１０％圧縮したときの圧縮弾性率及び３０％圧縮したときの圧縮弾性率）は、以下のようにして測定できる。 The 10% K value and 30% K value (compression elastic modulus when the resin particles are compressed by 10% and compression elastic modulus when the resin particles are compressed by 30%) can be measured as follows.
　微小圧縮試験機を用いて、円柱（直径１００μｍ、ダイヤモンド製）の平滑圧子端面で、２５℃において、圧縮速度０．３ｍＮ／秒、及び最大試験荷重２０ｍＮの条件下で樹脂粒子１個を圧縮する。このときの荷重値（Ｎ）及び圧縮変位（ｍｍ）を測定する。得られた測定値から、２５℃における１０％Ｋ値又は３０％Ｋ値を下記式により求めることができる。上記微小圧縮試験機として、例えば、島津製作所社製「微小圧縮試験機ＭＣＴ－Ｗ２００」、及びフィッシャー社製「フィッシャースコープＨ－１００」等が用いられる。上記樹脂粒子の１０％Ｋ値又は３０％Ｋ値は、任意に選択された５０個の樹脂粒子の１０％Ｋ値又は３０％Ｋ値を算術平均することにより、算出することが好ましい。 Using a micro-compression tester, one resin particle is compressed on a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) at 25 ° C. under conditions of a compression rate of 0.3 mN / sec and a maximum test load of 20 mN. . The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured value, a 10% K value or a 30% K value at 25 ° C. can be obtained by the following formula. As the above-mentioned micro compression tester, for example, “Micro compression tester MCT-W200” manufactured by Shimadzu Corporation, “Fischer Scope H-100” manufactured by Fisher, etc. are used. The 10% K value or 30% K value of the resin particles is preferably calculated by arithmetically averaging the 10% K value or 30% K value of 50 resin particles selected arbitrarily.
　１０％Ｋ値又は３０％Ｋ値（Ｎ／ｍｍ２）＝（３／２１／２）・Ｆ・Ｓ－３／２・Ｒ－１／２
　Ｆ：樹脂粒子が１０％圧縮変形したときの荷重値（Ｎ）又は３０％圧縮変形したときの荷重値（Ｎ）
　Ｓ：樹脂粒子が１０％圧縮変形したときの圧縮変位（ｍｍ）又は３０％圧縮変形したときの圧縮変位（ｍｍ）
　Ｒ：樹脂粒子の半径（ｍｍ） 10% K value or 30% K value (N / mm 2 ) = (3/2 1/2 ) · F · S −3 / 2 · R −1/2
F: Load value when the resin particles are 10% compressively deformed (N) or load value when the resin particles are 30% compressively deformed (N)
S: Compression displacement (mm) when resin particles are 10% compressively deformed or compression displacement (mm) when 30% compressively deformed
R: radius of resin particles (mm)
　上記Ｋ値は、樹脂粒子の硬さを普遍的かつ定量的に表す。上記Ｋ値を用いることにより、樹脂粒子の硬さを定量的かつ一義的に表すことができる。 The above K value represents the hardness of the resin particles universally and quantitatively. By using the K value, the hardness of the resin particles can be expressed quantitatively and uniquely.
　スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、樹脂粒子の６０％圧縮変形させた際の圧縮回復率は、好ましくは２％以上、より好ましくは４％以上であり、好ましくは１０％以下、より好ましくは９．５％以下、さらに好ましくは９％以下である。 From the viewpoint of more effectively suppressing the occurrence of spring back and the viewpoint of more effectively suppressing the occurrence of floating or peeling, the compression recovery rate when the resin particles are subjected to 60% compression deformation is preferably It is 2% or more, more preferably 4% or more, preferably 10% or less, more preferably 9.5% or less, and further preferably 9% or less.
　上記樹脂粒子の６０％圧縮変形させた際の圧縮回復率は、以下のようにして測定できる。 The compression recovery rate when the resin particles are 60% compressed and deformed can be measured as follows.
　試料台上に樹脂粒子を散布する。散布された樹脂粒子１個について、微小圧縮試験機を用いて、円柱（直径１００μｍ、ダイヤモンド製）の平滑圧子端面で、２５℃において、樹脂粒子の中心方向に、樹脂粒子が６０％圧縮変形するまで負荷（反転荷重値）を与える。その後、原点用荷重値（０．４０ｍＮ）まで除荷を行う。この間の荷重－圧縮変位を測定し、下記式から２５℃における６０％圧縮変形させた際の圧縮回復率を求めることができる。なお、負荷速度は０．３３ｍＮ／秒とする。上記微小圧縮試験機として、例えば、島津製作所社製「微小圧縮試験機ＭＣＴ－Ｗ２００」、及びフィッシャー社製「フィッシャースコープＨ－１００」等が用いられる。 ¡Spray resin particles on the sample stage. With respect to one dispersed resin particle, the resin particle is compressed and deformed by 60% in the center direction of the resin particle at 25 ° C. on a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) using a micro compression tester. Apply a load (reverse load value). Thereafter, unloading is performed up to the origin load value (0.40 mN). The load-compression displacement during this period is measured, and the compression recovery rate when 60% compression deformation at 25 ° C. is obtained from the following equation. The load speed is 0.33 mN / sec. As the above-mentioned micro compression tester, for example, “Micro compression tester MCT-W200” manufactured by Shimadzu Corporation, “Fischer Scope H-100” manufactured by Fisher, etc. are used.
　圧縮回復率（％）＝［Ｌ２／Ｌ１］×１００
　Ｌ１：負荷を与えるときの原点用荷重値から反転荷重値に至るまでの圧縮変位
　Ｌ２：負荷を解放するときの反転荷重値から原点用荷重値に至るまでの除荷変位 Compression recovery rate (%) = [L2 / L1] × 100
L1: Compressive displacement from the origin load value to the reverse load value when applying a load L2: Unloading displacement from the reverse load value to the origin load value when releasing the load
　上記樹脂粒子の用途は特に限定されない。上記樹脂粒子は、様々な用途に好適に用いられる。上記樹脂粒子は、スペーサとして用いられるか、又は導電部を有する導電性粒子を得るために用いられることが好ましい。上記導電性粒子において、上記導電部は、上記樹脂粒子の表面上に形成される。上記樹脂粒子は、スペーサとして用いられることが好ましい。上記樹脂粒子は、導電部を有する導電性粒子を得るために用いられることが好ましい。上記スペーサの使用方法としては、液晶表示素子用スペーサ、ギャップ制御用スペーサ、及び応力緩和用スペーサ等が挙げられる。上記ギャップ制御用スペーサは、スタンドオフ高さ及び平坦性を確保するための積層チップのギャップ制御、並びに、ガラス面の平滑性及び接着剤層の厚みを確保するための光学部品のギャップ制御等に用いることができる。上記応力緩和用スペーサは、センサチップ等の応力緩和、及び２つの接続対象部材を接続している接続部の応力緩和等に用いることができる。 The use of the resin particles is not particularly limited. The resin particles are suitably used for various applications. The resin particles are preferably used as spacers or to obtain conductive particles having a conductive part. In the conductive particle, the conductive portion is formed on the surface of the resin particle. The resin particles are preferably used as spacers. The resin particles are preferably used for obtaining conductive particles having a conductive part. Examples of the method of using the spacer include a liquid crystal display element spacer, a gap control spacer, and a stress relaxation spacer. The above spacer for gap control is used for gap control of laminated chips for ensuring standoff height and flatness, and for optical component gap control for ensuring smoothness of the glass surface and thickness of the adhesive layer. Can be used. The stress relaxation spacer can be used for stress relaxation of a sensor chip or the like, and stress relaxation of a connection portion connecting two connection target members.
　上記樹脂粒子は、液晶表示素子用スペーサとして用いられることが好ましく、液晶表示素子用周辺シール剤に用いられることが好ましい。上記液晶表示素子用周辺シール剤において、上記樹脂粒子は、スペーサとして機能することが好ましい。上記樹脂粒子は、良好な圧縮変形特性を有するので、上記樹脂粒子をスペーサとして用いて基板間に配置したり、表面に導電部を形成して導電性粒子として用いて電極間を電気的に接続したりした場合に、スペーサ又は導電性粒子が、基板間又は電極間に効率的に配置される。さらに、上記樹脂粒子では、液晶表示素子用部材等の傷付きを抑えることができるので、上記液晶表示素子用スペーサを用いた液晶表示素子及び上記導電性粒子を用いた接続構造体において、接続不良及び表示不良が生じ難くなる。 The resin particles are preferably used as spacers for liquid crystal display elements, and are preferably used as peripheral sealing agents for liquid crystal display elements. In the peripheral sealing agent for a liquid crystal display element, the resin particles preferably function as a spacer. Since the resin particles have good compressive deformation characteristics, the resin particles are used as spacers to be arranged between the substrates, or conductive parts are formed on the surface and used as conductive particles to electrically connect the electrodes. In such a case, spacers or conductive particles are efficiently disposed between the substrates or the electrodes. Furthermore, in the resin particles, since damage to the liquid crystal display element member and the like can be suppressed, connection failure in the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles. And display defects are less likely to occur.
　さらに、上記樹脂粒子は、無機充填材、トナーの添加剤、衝撃吸収剤又は振動吸収剤としても好適に用いられる。例えば、ゴム又はバネ等の代替品として、上記樹脂粒子を用いることができる。 Furthermore, the resin particles are also suitably used as an inorganic filler, a toner additive, a shock absorber or a vibration absorber. For example, the resin particles can be used as a substitute for rubber or a spring.
　（樹脂粒子のその他の詳細）
　本発明に係る樹脂粒子は、重合性官能基を１個有し、かつ環状有機基を有する第１の重合性化合物と、重合性官能基を２個以上有し、かつ環状有機基を有する第２の重合性化合物との重合体である。上記樹脂粒子は、上記第１の重合性化合物と、上記第２の重合性化合物とを重合させて得ることが好ましい。 (Other details of resin particles)
The resin particles according to the present invention include a first polymerizable compound having one polymerizable functional group and having a cyclic organic group, and two or more polymerizable functional groups and having a cyclic organic group. 2 is a polymer with a polymerizable compound. The resin particles are preferably obtained by polymerizing the first polymerizable compound and the second polymerizable compound.
　スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記樹脂粒子では、樹脂粒子の中心部と樹脂粒子の表面部とが同一の上記重合体で構成されていることが好ましい。上記樹脂粒子の中心部における重合性化合物の配合比と、上記樹脂粒子の表面部における重合性化合物の配合比とは、同一であってもよく、異なっていてもよい。上記樹脂粒子の中心部における構成成分の構成比と、上記樹脂粒子の表面部における構成成分の構成比とは、同一であってもよく、異なっていてもよい。 From the viewpoint of more effectively suppressing the occurrence of springback, and from the viewpoint of more effectively suppressing the occurrence of floating or peeling, the resin particles have a central portion of the resin particles and a surface portion of the resin particles. It is preferable that they are composed of the same polymer. The compounding ratio of the polymerizable compound in the central part of the resin particles and the compounding ratio of the polymerizable compound in the surface part of the resin particles may be the same or different. The constituent ratio of the constituent components in the central portion of the resin particles and the constituent ratio of the constituent components in the surface portion of the resin particles may be the same or different.
　上記樹脂粒子では、樹脂粒子の中心部が中心部形成材料により形成されており、樹脂粒子の表面部が表面部形成材料により形成されていることが好ましい。スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記樹脂粒子では、上記中心部形成材料の成分と上記表面部形成材料の成分とは、同一であることが好ましい。上記樹脂粒子では、上記中心部形成材料の成分比と上記表面部形成材料の成分比とは、同一であってもよく、異なっていてもよい。また、上記樹脂粒子では、上記中心部形成材料と上記表面部形成材料との双方を含む領域が存在することが好ましい。上記樹脂粒子では、上記中心部形成材料を含み、かつ上記表面部形成材料を含まないか又は上記表面部形成材料を２５％未満で含む領域を、樹脂粒子が中心部に有することが好ましい。上記樹脂粒子では、上記表面部形成材料を含み、かつ上記中心部形成材料を含まないか又は上記中心部形成材料を２５％未満で含む領域を、樹脂粒子が表面部に有することが好ましい。 In the resin particles, it is preferable that the center part of the resin particles is formed of the center part forming material, and the surface part of the resin particles is formed of the surface part forming material. From the viewpoint of more effectively suppressing the occurrence of springback and further effectively suppressing the occurrence of floating or peeling, in the resin particles, the component of the center portion forming material and the surface portion forming material are used. These components are preferably the same. In the resin particles, the component ratio of the central portion forming material and the component ratio of the surface portion forming material may be the same or different. In the resin particle, it is preferable that a region including both the center portion forming material and the surface portion forming material exists. In the resin particle, it is preferable that the resin particle has a region including the center portion forming material and not including the surface portion forming material or including the surface portion forming material in less than 25% in the center portion. In the resin particle, it is preferable that the resin particle has a region including the surface portion forming material and not including the center portion forming material or including the center portion forming material in less than 25% in the surface portion.
　上記樹脂粒子は、コアと、該コアの表面上に配置されたシェルとを備えるコアシェル粒子ではないことが好ましく、樹脂粒子内で、コアとシェルとの界面を有さないことが好ましい。上記樹脂粒子は、樹脂粒子内で、界面を有さないことが好ましく、異なる面同士が接触している界面を有さないことがより好ましい。上記樹脂粒子は、表面が存在する不連続部分を有さないことが好ましく、構造表面が存在する不連続部分を有さないことが好ましい。 The resin particle is preferably not a core-shell particle including a core and a shell disposed on the surface of the core, and preferably does not have an interface between the core and the shell in the resin particle. The resin particles preferably do not have an interface in the resin particles, and more preferably do not have an interface in which different surfaces are in contact with each other. The resin particles preferably do not have a discontinuous portion where a surface exists, and preferably do not have a discontinuous portion where a structural surface exists.
　本発明に係る樹脂粒子では、上記第１の重合性化合物は、重合性官能基（第１の重合性官能基）を１個有する。上記重合性官能基（第１の重合性官能基）としては特に限定されず、例えば、ビニル基、アクリロイル基及びメタクリロイル基等が挙げられる。上記第１の重合性化合物としては、スチレン、メタクリル酸フェニル、アクリル酸フェニル、メタクリル酸シクロヘキシル、アクリル酸シクロヘキシル、イソボルニルメタクリレート及びイソボルニルアクリレート等が挙げられる。上記第１の重合性化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 In the resin particles according to the present invention, the first polymerizable compound has one polymerizable functional group (first polymerizable functional group). The polymerizable functional group (first polymerizable functional group) is not particularly limited, and examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group. Examples of the first polymerizable compound include styrene, phenyl methacrylate, phenyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, and isobornyl acrylate. As for the said 1st polymeric compound, only 1 type may be used and 2 or more types may be used together.
　本発明に係る樹脂粒子では、上記第２の重合性化合物は、重合性官能基（第２の重合性官能基）を２個以上有する。上記重合性官能基（第２の重合性官能基）としては特に限定されず、例えば、ビニル基、アクリロイル基及びメタクリロイル基等が挙げられる。上記第２の重合性化合物としては、ジビニルベンゼン、ジビニルナフタレン、ジビニルシクロヘキサン、及びトリビニルシクロヘキサン等が挙げられる。上記第２の重合性化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 In the resin particles according to the present invention, the second polymerizable compound has two or more polymerizable functional groups (second polymerizable functional groups). The polymerizable functional group (second polymerizable functional group) is not particularly limited, and examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group. Examples of the second polymerizable compound include divinylbenzene, divinylnaphthalene, divinylcyclohexane, and trivinylcyclohexane. As for the said 2nd polymeric compound, only 1 type may be used and 2 or more types may be used together.
　上記樹脂粒子は、上記第１の重合性化合物と上記第２の重合性化合物とを重量比（第１の重合性化合物の重量／第２の重合性化合物の重量）で、好ましくは７以上、より好ましくは９以上、さらに好ましくは１３以上、好ましくは２０以下、より好ましくは１８．５以下、さらに好ましくは１７以下で重合させて得ることがさらに好ましい。上記樹脂粒子は、上記第１の重合性化合物と上記第２の重合性化合物とを重量比で、７以上で重合させて得ることが好ましく、９以上で重合させて得ることがより好ましく、１３以上で重合させて得ることがさらに好ましい。上記樹脂粒子は、上記第１の重合性化合物と上記第２の重合性化合物とを重量比で、２０以下で重合させて得ることが好ましく、１８．５以下で重合させて得ることがより好ましく、１７以下で重合させて得ることがさらに好ましい。上記樹脂粒子は、上記第１の重合性化合物と上記第２の重合性化合物とを上記の好ましい範囲の重量比で重合させて得ることにより、スプリングバックの発生をより一層効果的に抑制することができ、かつ、浮き又は剥離の発生をより一層効果的に抑制することができる。 The resin particles preferably have a weight ratio of the first polymerizable compound and the second polymerizable compound (weight of the first polymerizable compound / weight of the second polymerizable compound), preferably 7 or more. More preferably, it is more preferably 9 or more, further preferably 13 or more, preferably 20 or less, more preferably 18.5 or less, and still more preferably 17 or less. The resin particles are preferably obtained by polymerizing the first polymerizable compound and the second polymerizable compound at a weight ratio of 7 or more, more preferably 9 or more. It is more preferable to obtain the polymer by the above. The resin particles are preferably obtained by polymerizing the first polymerizable compound and the second polymerizable compound at a weight ratio of 20 or less, more preferably 18.5 or less. More preferably, it is obtained by polymerization at 17 or less. The resin particles are obtained by polymerizing the first polymerizable compound and the second polymerizable compound at a weight ratio in the above preferable range, thereby more effectively suppressing the occurrence of springback. And the occurrence of floating or peeling can be more effectively suppressed.
　本発明に係る樹脂粒子は、２種以上の環状有機基を含むことが好ましい。本発明に係る樹脂粒子では、上記第１の重合性化合物は環状有機基（第１の環状有機基）を有する。上記第１の重合性化合物は環状有機基を１個以上有する。本発明に係る樹脂粒子では、上記第２の重合性化合物は環状有機基（第２の環状有機基）を有する。上記第２の重合性化合物は環状有機基を１個以上有する。本発明に係る樹脂粒子では、上記第１の重合性化合物における環状有機基（第１の環状有機基）と上記第２の重合性化合物における環状有機基（第２の環状有機基）とは同一であってもよく、異なっていてもよい。上記第１の重合性化合物における環状有機基（第１の環状有機基）と上記第２の重合性化合物における環状有機基（第２の環状有機基）とは、異なることが好ましい。 The resin particles according to the present invention preferably contain two or more kinds of cyclic organic groups. In the resin particles according to the present invention, the first polymerizable compound has a cyclic organic group (first cyclic organic group). The first polymerizable compound has one or more cyclic organic groups. In the resin particle according to the present invention, the second polymerizable compound has a cyclic organic group (second cyclic organic group). The second polymerizable compound has one or more cyclic organic groups. In the resin particle according to the present invention, the cyclic organic group (first cyclic organic group) in the first polymerizable compound and the cyclic organic group (second cyclic organic group) in the second polymerizable compound are the same. May be different. It is preferable that the cyclic organic group (first cyclic organic group) in the first polymerizable compound and the cyclic organic group (second cyclic organic group) in the second polymerizable compound are different.
　スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記第１の重合性化合物における環状有機基（第１の環状有機基）と上記第２の重合性化合物における環状有機基（第２の環状有機基）とがそれぞれ、炭化水素基であることが好ましい。 From the viewpoint of more effectively suppressing the occurrence of spring back and the viewpoint of more effectively suppressing the occurrence of floating or peeling, a cyclic organic group (first cyclic organic group) in the first polymerizable compound is used. ) And the cyclic organic group (second cyclic organic group) in the second polymerizable compound are each preferably a hydrocarbon group.
　上記炭化水素基としては、フェニル基、フェニレン基、ナフチル基、ナフチレン基、シクロプロピル基、シクロヘキシル基、イソボルニル基、及びジシクロペンタニル基等が挙げられる。 Examples of the hydrocarbon group include a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, a cyclopropyl group, a cyclohexyl group, an isobornyl group, and a dicyclopentanyl group.
　スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、本発明に係る樹脂粒子は、フェニレン基、シクロヘキシル基又はイソボルニル基の中の２個以上の環状有機基を有することが好ましい。 From the viewpoint of more effectively suppressing the occurrence of springback and further effectively suppressing the occurrence of floating or peeling, the resin particles according to the present invention have a phenylene group, a cyclohexyl group or an isobornyl group. It is preferable to have two or more cyclic organic groups.
　スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記第１の重合性化合物における環状有機基（第１の環状有機基）は、フェニレン基、シクロヘキシル基又はイソボルニル基であることが好ましい。 From the viewpoint of more effectively suppressing the occurrence of spring back and the viewpoint of more effectively suppressing the occurrence of floating or peeling, a cyclic organic group (first cyclic organic group) in the first polymerizable compound is used. ) Is preferably a phenylene group, a cyclohexyl group or an isobornyl group.
　スプリングバックの発生をより一層効果的に抑制する観点、及び浮き又は剥離の発生をより一層効果的に抑制する観点からは、上記第２の重合性化合物における環状有機基（第２の環状有機基）は、フェニレン基、シクロヘキシル基又はイソボルニル基であることが好ましい。 From the viewpoint of more effectively suppressing the occurrence of springback and the viewpoint of more effectively suppressing the occurrence of floating or peeling, a cyclic organic group (second cyclic organic group) in the second polymerizable compound is used. ) Is preferably a phenylene group, a cyclohexyl group or an isobornyl group.
　上記樹脂粒子が導電性粒子として用いられる場合において、樹脂粒子とめっきとの密着性をより一層効果的に高める観点からは、上記樹脂粒子は、アシッドホスフェート化合物を含むことが好ましい。上記樹脂粒子は、表面上にアシッドホスフェート化合物に由来するリン酸構造を有することが好ましい。上記樹脂粒子が表面上に上記リン酸構造を有することで、めっきとの密着性をより一層効果的に高めることができる。さらに、上記樹脂粒子が表面上に上記リン酸構造を有することで、上記樹脂粒子が加熱によって収縮したとしても、めっき割れをより一層効果的に抑制することができる。例えば、アシッドホスフェート化合物を含む樹脂粒子を無電解めっきすることにより作製した導電性粒子と、バインダーとを含む導電材料では、電極間の接続の際に加熱されたり、導電材料が加熱環境に曝されたりしたとしても、めっき割れをより一層効果的に抑制することができ、電極間の接続信頼性をより一層効果的に高めることができる。上記樹脂粒子が導電性粒子を得るために用いられる場合には、上記樹脂粒子は、アシッドホスフェート化合物を含むことが好ましい。上記樹脂粒子が導電性粒子を得るために用いられる場合には、上記樹脂粒子は、表面上にアシッドホスフェート化合物に由来するリン酸構造を有することが好ましい。上記アシッドホスフェート化合物は、酸性リン酸エステル化合物であることが好ましい。 In the case where the resin particles are used as conductive particles, the resin particles preferably contain an acid phosphate compound from the viewpoint of further effectively improving the adhesion between the resin particles and the plating. The resin particles preferably have a phosphoric acid structure derived from an acid phosphate compound on the surface. When the resin particles have the phosphoric acid structure on the surface, the adhesion with the plating can be further effectively improved. Furthermore, since the resin particles have the phosphoric acid structure on the surface, plating cracks can be more effectively suppressed even when the resin particles shrink due to heating. For example, in a conductive material containing conductive particles produced by electroless plating of resin particles containing an acid phosphate compound and a binder, the conductive material is heated when the electrodes are connected, or the conductive material is exposed to a heating environment. Even if it does, a plating crack can be suppressed still more effectively and the connection reliability between electrodes can be improved much more effectively. When the resin particles are used for obtaining conductive particles, the resin particles preferably contain an acid phosphate compound. When the resin particles are used to obtain conductive particles, the resin particles preferably have a phosphoric acid structure derived from an acid phosphate compound on the surface. The acid phosphate compound is preferably an acidic phosphate compound.
　上記アシッドホスフェート化合物としては、エチルアシッドホスフェート、ブチルアシッドホスフェート、ブトキシエチルアシッドホスフェート、２－エチルヘキシルアシッドホスフェート、イソトリデシルアシッドホスフェート、オレイルアシッドホスフェート、テトラコシルアシッドホスフェート、エチレングリコールアシッドホスフェート、２－ヒドロキシエチルメタクリルアシッドホスフェート、ジブチルアシッドホスフェート、及びビス（２－エチルヘキシル）アシッドホスフェート等が挙げられる。上記アシッドホスフェート化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the acid phosphate compound include ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxy acid phosphate Examples thereof include ethyl methacrylic acid phosphate, dibutyl acid phosphate, and bis (2-ethylhexyl) acid phosphate. As for the said acid phosphate compound, only 1 type may be used and 2 or more types may be used together.
　樹脂粒子とめっきとの密着性をより一層効果的に高める観点からは、上記樹脂粒子１００重量％中、上記アシッドホスフェート化合物の含有量は、好ましくは１重量％以上、より好ましくは５重量％以上であり、好ましくは２０重量％以下、より好ましくは１５重量％以下である。 From the viewpoint of more effectively increasing the adhesion between the resin particles and the plating, the content of the acid phosphate compound in 100% by weight of the resin particles is preferably 1% by weight or more, more preferably 5% by weight or more. And preferably 20% by weight or less, more preferably 15% by weight or less.
　（導電性粒子）
　本発明に係る導電性粒子は、上述した樹脂粒子と、該樹脂粒子の表面上に配置された導電部とを備える。 (Conductive particles)
The electroconductive particle which concerns on this invention is equipped with the resin particle mentioned above and the electroconductive part arrange | positioned on the surface of this resin particle.
　図１は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。 FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
　図１に示す導電性粒子１は、樹脂粒子１１と、樹脂粒子１１の表面上に配置された導電部２とを有する。導電部２は、樹脂粒子１１の表面に接している。導電部２は、樹脂粒子１１の表面を覆っている。導電性粒子１は、樹脂粒子１１の表面が導電部２により被覆された被覆粒子である。導電性粒子１では、導電部２は、単層の導電部（導電層）である。 1 has resin particles 11 and a conductive portion 2 disposed on the surface of the resin particles 11. The conductive particles 1 shown in FIG. The conductive part 2 is in contact with the surface of the resin particle 11. The conductive part 2 covers the surface of the resin particle 11. The conductive particle 1 is a coated particle in which the surface of the resin particle 11 is covered with the conductive part 2. In the conductive particles 1, the conductive part 2 is a single-layer conductive part (conductive layer).
　図２は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。 FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
　図２に示す導電性粒子２１は、樹脂粒子１１と、樹脂粒子１１の表面上に配置された導電部２２とを有する。導電部２２は全体で、樹脂粒子１１側に第１の導電部２２Ａと、樹脂粒子１１側とは反対側に第２の導電部２２Ｂとを有する。 2 has resin particles 11 and conductive portions 22 arranged on the surface of the resin particles 11. The conductive particles 21 shown in FIG. The conductive part 22 as a whole has a first conductive part 22A on the resin particle 11 side and a second conductive part 22B on the opposite side to the resin particle 11 side.
　図１に示す導電性粒子１と図２に示す導電性粒子２１とでは、導電部２２のみが異なっている。すなわち、導電性粒子１では、１層構造の導電部が形成されているのに対し、導電性粒子２１では、２層構造の第１の導電部２２Ａ及び第２の導電部２２Ｂが形成されている。第１の導電部２２Ａと第２の導電部２２Ｂとは、異なる導電部として形成されていてもよく、同一の導電部として形成されていてもよい。 1 is different from the conductive particles 1 shown in FIG. 1 only in the conductive portion 22. That is, in the conductive particle 1, a conductive portion having a single layer structure is formed, whereas in the conductive particle 21, a first conductive portion 22A and a second conductive portion 22B having a two layer structure are formed. Yes. The first conductive portion 22A and the second conductive portion 22B may be formed as different conductive portions or may be formed as the same conductive portion.
　第１の導電部２２Ａは、樹脂粒子１１の表面上に配置されている。樹脂粒子１１と第２の導電部２２Ｂとの間に、第１の導電部２２Ａが配置されている。第１の導電部２２Ａは、樹脂粒子１１に接している。第２の導電部２２Ｂは、第１の導電部２２Ａに接している。樹脂粒子１１の表面上に第１の導電部２２Ａが配置されており、第１の導電部２２Ａの表面上に第２の導電部２２Ｂが配置されている。 The first conductive part 22 </ b> A is disposed on the surface of the resin particle 11. A first conductive portion 22A is disposed between the resin particle 11 and the second conductive portion 22B. The first conductive portion 22 </ b> A is in contact with the resin particle 11. The second conductive portion 22B is in contact with the first conductive portion 22A. The first conductive portion 22A is disposed on the surface of the resin particle 11, and the second conductive portion 22B is disposed on the surface of the first conductive portion 22A.
　図３は、本発明の第３の実施形態に係る導電性粒子を示す断面図である。 FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
　図３に示す導電性粒子３１は、樹脂粒子１１と、導電部３２と、複数の芯物質３３と、複数の絶縁性物質３４とを有する。導電部３２は、樹脂粒子１１の表面上に配置されている。複数の芯物質３３は、樹脂粒子１１の表面上に配置されている。導電部３２は、樹脂粒子１１と、複数の芯物質３３とを覆うように、樹脂粒子１１の表面上に配置されている。導電性粒子３１では、導電部３２は、単層の導電部（導電層）である。 3 includes resin particles 11, a conductive portion 32, a plurality of core materials 33, and a plurality of insulating materials 34. The conductive portion 32 is disposed on the surface of the resin particle 11. The plurality of core substances 33 are arranged on the surface of the resin particles 11. The conductive portion 32 is disposed on the surface of the resin particle 11 so as to cover the resin particle 11 and the plurality of core substances 33. In the conductive particles 31, the conductive portion 32 is a single-layer conductive portion (conductive layer).
　導電性粒子３１は外表面に、複数の突起３１ａを有する。導電性粒子３１では、導電部３２は外表面に、複数の突起３２ａを有する。複数の芯物質３３は、導電部３２の外表面を隆起させている。導電部３２の外表面が複数の芯物質３３によって隆起されていることで、突起３１ａ及び３２ａが形成されている。複数の芯物質３３は導電部３２内に埋め込まれている。突起３１ａ及び３２ａの内側に、芯物質３３が配置されている。導電性粒子３１では、突起３１ａ及び３２ａを形成するために、複数の芯物質３３を用いている。上記導電性粒子では、上記突起を形成するために、複数の上記芯物質を用いなくてもよい。上記導電性粒子は、複数の上記芯物質を備えていなくてもよい。 The conductive particles 31 have a plurality of protrusions 31a on the outer surface. In the conductive particles 31, the conductive portion 32 has a plurality of protrusions 32a on the outer surface. The plurality of core materials 33 raise the outer surface of the conductive portion 32. Since the outer surface of the conductive portion 32 is raised by a plurality of core materials 33, the protrusions 31a and 32a are formed. The plurality of core materials 33 are embedded in the conductive portion 32. A core substance 33 is disposed inside the protrusions 31a and 32a. In the conductive particles 31, a plurality of core materials 33 are used to form the protrusions 31a and 32a. In the conductive particles, a plurality of the core substances may not be used to form the protrusions. The conductive particles may not include a plurality of the core substances.
　導電性粒子３１は、導電部３２の外表面上に配置された絶縁性物質３４を有する。導電部３２の外表面の少なくとも一部の領域が、絶縁性物質３４により被覆されている。絶縁性物質３４は絶縁性を有する材料により形成されており、絶縁性粒子である。このように、本発明に係る導電性粒子は、導電部の外表面上に配置された絶縁性物質を有していてもよい。但し、上記導電性粒子は、絶縁性物質を必ずしも有していなくてもよい。上記導電性粒子は、複数の絶縁性物質を備えていなくてもよい。 The conductive particles 31 have an insulating substance 34 disposed on the outer surface of the conductive portion 32. At least a part of the outer surface of the conductive portion 32 is covered with an insulating material 34. The insulating substance 34 is made of an insulating material and is an insulating particle. Thus, the electroconductive particle which concerns on this invention may have the insulating substance arrange | positioned on the outer surface of an electroconductive part. However, the conductive particles do not necessarily have an insulating material. The conductive particles may not include a plurality of insulating substances.
　導電部：
　上記導電部を形成するための金属は特に限定されない。該金属としては、例えば、金、銀、パラジウム、銅、白金、亜鉛、鉄、錫、鉛、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、タリウム、ゲルマニウム、カドミウム、ケイ素、タングステン、モリブデン及びこれらの合金等が挙げられる。また、上記金属としては、錫ドープ酸化インジウム（ＩＴＯ）及びはんだ等が挙げられる。電極間の接続抵抗をより一層低くすることができるので、錫を含む合金、ニッケル、パラジウム、銅又は金が好ましく、ニッケル又はパラジウムが好ましい。 Conductive part:
The metal for forming the conductive part is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and tungsten. , Molybdenum, and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. Since the connection resistance between the electrodes can be further reduced, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.
　また、導通信頼性を効果的に高めることができるので、上記導電部及び上記導電部の外表面部分はニッケルを含むことが好ましい。ニッケルを含む導電部１００重量％中のニッケルの含有量は、好ましくは１０重量％以上、より好ましくは５０重量％以上、より一層好ましくは６０重量％以上、さらに好ましくは７０重量％以上、特に好ましくは９０重量％以上である。上記ニッケルを含む導電部１００重量％中のニッケルの含有量は、９７重量％以上であってもよく、９７．５重量％以上であってもよく、９８重量％以上であってもよい。 Also, since the conduction reliability can be effectively improved, it is preferable that the conductive portion and the outer surface portion of the conductive portion contain nickel. The content of nickel in 100% by weight of the conductive part containing nickel is preferably 10% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, particularly preferably. Is 90% by weight or more. The content of nickel in 100% by weight of the conductive part containing nickel may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.
　なお、導電部の表面には、酸化により水酸基が存在することが多い。一般的に、ニッケルにより形成された導電部の表面には、酸化により水酸基が存在する。このような水酸基を有する導電部の表面（導電性粒子の表面）に、化学結合を介して、絶縁性物質を配置することができる。 In many cases, hydroxyl groups are present on the surface of the conductive part due to oxidation. In general, a hydroxyl group exists on the surface of a conductive portion formed of nickel by oxidation. An insulating substance can be disposed on the surface of the conductive part having such a hydroxyl group (the surface of the conductive particle) through a chemical bond.
　導電性粒子１，３１のように、上記導電部は、１つの層により形成されていてもよい。導電性粒子２１のように、導電部は、複数の層により形成されていてもよい。すなわち、導電部は、２層以上の積層構造を有していてもよい。導電部が複数の層により形成されている場合には、最外層は、金層、ニッケル層、パラジウム層、銅層又は錫と銀とを含む合金層であることが好ましく、金層であることがより好ましい。最外層がこれらの好ましい導電部である場合には、電極間の接続抵抗をより一層効果的に低くすることができる。また、最外層が金層である場合には、耐腐食性をより一層効果的に高めることができる。 Like the conductive particles 1 and 31, the conductive part may be formed of a single layer. Like the electroconductive particle 21, the electroconductive part may be formed of the some layer. That is, the conductive part may have a laminated structure of two or more layers. When the conductive portion is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable. When the outermost layer is such a preferable conductive portion, the connection resistance between the electrodes can be further effectively reduced. Further, when the outermost layer is a gold layer, the corrosion resistance can be further effectively improved.
　上記樹脂粒子の表面に上記導電部を形成する方法は特に限定されない。上記導電部を形成する方法としては、例えば、無電解めっきによる方法、電気めっきによる方法、物理的蒸着による方法、並びに金属粉末もしくは金属粉末とバインダーとを含むペーストを樹脂粒子の表面にコーティングする方法等が挙げられる。導電部の形成が簡便であるので、無電解めっきによる方法が好ましい。上記物理的蒸着による方法としては、真空蒸着、イオンプレーティング及びイオンスパッタリング等の方法が挙げられる。 The method for forming the conductive part on the surface of the resin particles is not particularly limited. Examples of the method for forming the conductive part include a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of resin particles with a metal powder or a paste containing a metal powder and a binder. Etc. Since formation of the conductive part is simple, a method by electroless plating is preferred. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
　上記導電性粒子の粒子径は、好ましくは０．５μｍ以上、より好ましくは１．０μｍ以上であり、好ましくは５００μｍ以下、より好ましくは４５０μｍ以下、より一層好ましくは１００μｍ以下、さらに好ましくは５０μｍ以下、特に好ましくは２０μｍ以下である。上記導電性粒子の粒子径が、上記下限以上及び上記上限以下であると、導電性粒子を用いて電極間を接続した場合に、導電性粒子と電極との接触面積が十分に大きくなり、かつ導電部を形成する際に凝集した導電性粒子が形成され難くなる。また、導電性粒子を介して接続された電極間の間隔が大きくなりすぎず、かつ導電部が樹脂粒子の表面から剥離し難くなる。また、上記導電性粒子の粒子径が、上記下限以上及び上記上限以下であると、導電性粒子を導電材料の用途に好適に使用可能である。 The particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 500 μm or less, more preferably 450 μm or less, still more preferably 100 μm or less, still more preferably 50 μm or less, Particularly preferably, it is 20 μm or less. When the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes becomes sufficiently large, and Aggregated conductive particles are hardly formed when the conductive portion is formed. In addition, the interval between the electrodes connected via the conductive particles does not become too large, and the conductive portion is difficult to peel from the surface of the resin particles. Further, when the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of a conductive material.
　上記導電性粒子の粒子径は、導電性粒子が真球状である場合には、直径を示し、導電性粒子が真球状ではない場合には、最大径を示す。 The particle diameter of the conductive particles indicates the diameter when the conductive particles are true spherical, and indicates the maximum diameter when the conductive particles are not true spherical.
　上記導電性粒子の粒子径は、平均粒子径であることが好ましく、数平均粒子径であることがより好ましい。上記導電性粒子の粒子径は、例えば、任意の導電性粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することや、複数回のレーザー回折式粒度分布測定装置による測定結果の平均値を算出することにより求められる。 The particle diameter of the conductive particles is preferably an average particle diameter, and more preferably a number average particle diameter. The particle diameter of the conductive particles is, for example, observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or a measurement result obtained by a plurality of laser diffraction particle size distribution measuring devices. It is calculated | required by calculating the average value of.
　上記導電部の厚みは、好ましくは０．００５μｍ以上、より好ましくは０．０１μｍ以上であり、好ましくは１０μｍ以下、より好ましくは１μｍ以下、さらに好ましくは０．３μｍ以下である。上記導電部の厚みが、上記下限以上及び上記上限以下であると、十分な導電性が得られ、かつ導電性粒子が硬くなりすぎずに、電極間の接続の際に導電性粒子が十分に変形する。 The thickness of the conductive part is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 0.3 μm or less. When the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently bonded at the time of connection between the electrodes. Deform.
　上記導電部が複数の層により形成されている場合に、最外層の導電部の厚みは、好ましくは０．００１μｍ以上、より好ましくは０．０１μｍ以上であり、好ましくは０．５μｍ以下、より好ましくは０．１μｍ以下である。上記最外層の導電部の厚みが、上記下限以上及び上記上限以下であると、最外層の導電部による被覆が均一になり、耐腐食性が十分に高くなり、かつ電極間の接続抵抗が十分に低くなる。また、上記最外層が金層である場合に、金層の厚みが薄いほど、コストが低くなる。 When the conductive part is formed of a plurality of layers, the thickness of the conductive part of the outermost layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably Is 0.1 μm or less. When the thickness of the conductive portion of the outermost layer is not less than the above lower limit and not more than the above upper limit, the coating by the conductive portion of the outermost layer becomes uniform, corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficient It becomes low. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.
　上記導電部の厚みは、例えば透過型電子顕微鏡（ＴＥＭ）を用いて、導電性粒子の断面を観察することにより測定できる。上記導電部の厚みについては、任意の導電部の厚み５箇所の平均値を１個の導電性粒子の導電部の厚みとして算出することが好ましく、導電部全体の厚みの平均値を１個の導電部の厚みとして算出することがより好ましい。複数の導電性粒子の場合には、上記導電部の厚みは、好ましくは、任意の導電性粒子１０個について、これらの平均値を算出して求められる。 The thickness of the conductive part can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM). About the thickness of the said electroconductive part, it is preferable to calculate the average value of the thickness of five places of arbitrary electroconductive parts as the thickness of the electroconductive part of one electroconductive particle, and the average value of the thickness of the whole electroconductive part is 1 piece. It is more preferable to calculate the thickness of the conductive part. In the case of a plurality of conductive particles, the thickness of the conductive portion is preferably obtained by calculating an average value of 10 arbitrary conductive particles.
　芯物質：
　上記導電性粒子は、上記導電部の外表面に複数の突起を有することが好ましい。上記導電性粒子が、上記導電部の外表面に複数の突起を有していることで、電極間の導通信頼性をより一層高めることができる。上記導電性粒子により接続される電極の表面には、酸化被膜が形成されていることが多い。さらに、上記導電性粒子の導電部の表面には、酸化被膜が形成されていることが多い。上記突起を有する導電性粒子を用いることで、電極間に導電性粒子を配置した後、圧着させることにより、突起により酸化被膜が効果的に排除される。このため、電極と導電性粒子とをより一層確実に接触させることができ、電極間の接続抵抗をより一層効果的に低くすることができる。さらに、上記導電性粒子が表面に絶縁性物質を有する場合、又は導電性粒子がバインダー樹脂中に分散されて導電材料として用いられる場合に、導電性粒子の突起によって、導電性粒子と電極との間の絶縁性物質やバインダー樹脂が効果的に排除される。このため、電極間の導通信頼性をより一層効果的に高めることができる。 Core material:
The conductive particles preferably have a plurality of protrusions on the outer surface of the conductive part. Since the conductive particles have a plurality of protrusions on the outer surface of the conductive part, the conduction reliability between the electrodes can be further improved. An oxide film is often formed on the surface of the electrode connected by the conductive particles. Furthermore, an oxide film is often formed on the surface of the conductive part of the conductive particles. By using the conductive particles having the protrusions, the oxide film is effectively excluded by the protrusions by placing the conductive particles between the electrodes and then pressing them. For this reason, an electrode and electroconductive particle can be made to contact still more reliably, and the connection resistance between electrodes can be made still more effective. Furthermore, when the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the conductive particles and the electrodes are separated by protrusions of the conductive particles. Insulating substances and binder resins are effectively eliminated. For this reason, the conduction | electrical_connection reliability between electrodes can be improved much more effectively.
　上記芯物質が上記導電部中に埋め込まれていることによって、上記導電部の外表面に複数の突起を容易に形成することができる。但し、導電性粒子の導電部の表面に突起を形成するために、芯物質を必ずしも用いなくてもよい。 By embedding the core substance in the conductive part, a plurality of protrusions can be easily formed on the outer surface of the conductive part. However, the core substance is not necessarily used in order to form the protrusion on the surface of the conductive portion of the conductive particle.
　上記突起を形成する方法としては、樹脂粒子の表面に芯物質を付着させた後、無電解めっきにより導電部を形成する方法、並びに樹脂粒子の表面に無電解めっきにより導電部を形成した後、芯物質を付着させ、さらに無電解めっきにより導電部を形成する方法等が挙げられる。上記突起を形成する他の方法としては、樹脂粒子の表面上に、第１の導電部を形成した後、該第１の導電部上に芯物質を配置し、次に第２の導電部を形成する方法、並びに樹脂粒子の表面上に導電部（第１の導電部又は第２の導電部等）を形成する途中段階で、芯物質を添加する方法等が挙げられる。また、突起を形成するために、上記芯物質を用いずに、樹脂粒子に無電解めっきにより導電部を形成した後、導電部の表面上に突起状にめっきを析出させ、さらに無電解めっきにより導電部を形成する方法等を用いてもよい。 As a method of forming the protrusion, after a core material is attached to the surface of the resin particle, a method of forming a conductive part by electroless plating, and after forming a conductive part by electroless plating on the surface of the resin particle, Examples include a method of attaching a core substance and further forming a conductive portion by electroless plating. As another method of forming the protrusion, after forming the first conductive portion on the surface of the resin particle, a core substance is disposed on the first conductive portion, and then the second conductive portion is formed. Examples thereof include a forming method and a method of adding a core substance in the middle of forming a conductive portion (such as a first conductive portion or a second conductive portion) on the surface of the resin particle. Further, in order to form the protrusion, the conductive material is formed on the resin particles by electroless plating without using the core material, and then plating is deposited on the surface of the conductive portion in a protruding shape, and further, by electroless plating. A method of forming a conductive portion or the like may be used.
　上記樹脂粒子の表面上に芯物質を配置する方法としては、例えば、樹脂粒子の分散液中に、芯物質を添加し、樹脂粒子の表面に芯物質を、ファンデルワールス力により集積させ、付着させる方法、並びに樹脂粒子を入れた容器に、芯物質を添加し、容器の回転等による機械的な作用により樹脂粒子の表面に芯物質を付着させる方法等が挙げられる。付着させる芯物質の量を制御しやすいため、分散液中の樹脂粒子の表面に芯物質を集積させ、付着させる方法が好ましい。 As a method for disposing the core substance on the surface of the resin particles, for example, the core substance is added to the dispersion of resin particles, and the core substance is accumulated on the surface of the resin particles by van der Waals force and adhered. And a method of adding a core substance to a container containing resin particles and attaching the core substance to the surface of the resin particles by a mechanical action such as rotation of the container. Since it is easy to control the amount of the core material to be attached, a method in which the core material is accumulated on the surface of the resin particles in the dispersion and attached is preferable.
　上記芯物質の材料は特に限定されない。上記芯物質の材料としては、例えば、導電性物質及び非導電性物質が挙げられる。上記導電性物質としては、金属、金属の酸化物、黒鉛等の導電性非金属及び導電性ポリマー等が挙げられる。上記導電性ポリマーとしては、ポリアセチレン等が挙げられる。上記非導電性物質としては、シリカ、アルミナ、チタン酸バリウム及びジルコニア等が挙げられる。導電性を高めることができ、さらに接続抵抗を効果的に低くすることができるので、金属が好ましい。上記芯物質は金属粒子であることが好ましい。上記芯物質の材料である金属としては、上記導電部を形成するための金属として挙げた金属を適宜使用可能である。 The material of the core substance is not particularly limited. Examples of the material of the core substance include a conductive substance and a non-conductive substance. Examples of the conductive substance include metals, metal oxides, conductive non-metals such as graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene. Examples of the non-conductive substance include silica, alumina, barium titanate, zirconia, and the like. A metal is preferable because conductivity can be increased and connection resistance can be effectively reduced. The core substance is preferably metal particles. As the metal that is the material of the core substance, the metals mentioned as the metal for forming the conductive part can be used as appropriate.
　絶縁性物質：
　上記導電性粒子は、上記導電部の表面上に配置された絶縁性物質を備えることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡をより一層防止できる。具体的には、複数の導電性粒子が接触したときに、複数の電極間に絶縁性物質が存在するので、上下の電極間ではなく横方向に隣り合う電極間の短絡を防止できる。なお、電極間の接続の際に、２つの電極で導電性粒子を加圧することにより、導電性粒子の導電部と電極との間の絶縁性物質を容易に排除できる。上記導電性粒子が導電部の外表面に複数の突起を有する場合には、導電性粒子の導電部と電極との間の絶縁性物質をより一層容易に排除できる。 Insulating material:
The conductive particles preferably include an insulating material disposed on the surface of the conductive part. In this case, when the conductive particles are used for connection between the electrodes, a short circuit between adjacent electrodes can be further prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes. It should be noted that the insulating material between the conductive portion of the conductive particles and the electrode can be easily removed by pressurizing the conductive particles with the two electrodes when connecting the electrodes. When the conductive particles have a plurality of protrusions on the outer surface of the conductive part, the insulating substance between the conductive part of the conductive particles and the electrode can be more easily removed.
　電極間の圧着時に上記絶縁性物質をより一層容易に排除できることから、上記絶縁性物質は、絶縁性粒子であることが好ましい。 The insulating substance is preferably an insulating particle because the insulating substance can be more easily removed during crimping between the electrodes.
　上記絶縁性物質の材料としては、ポリオレフィン化合物、（メタ）アクリレート重合体、（メタ）アクリレート共重合体、ブロックポリマー、熱可塑性樹脂、熱可塑性樹脂の架橋物、熱硬化性樹脂及び水溶性樹脂等が挙げられる。上記絶縁性物質の材料は、１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the insulating material include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, thermosetting resins, water-soluble resins, and the like. Is mentioned. Only 1 type may be used for the material of the said insulating substance, and 2 or more types may be used together.
　上記ポリオレフィン化合物としては、ポリエチレン、エチレン－酢酸ビニル共重合体及びエチレン－アクリル酸エステル共重合体等が挙げられる。上記（メタ）アクリレート重合体としては、ポリメチル（メタ）アクリレート、ポリドデシル（メタ）アクリレート及びポリステアリル（メタ）アクリレート等が挙げられる。上記ブロックポリマーとしては、ポリスチレン、スチレン－アクリル酸エステル共重合体、ＳＢ型スチレン－ブタジエンブロック共重合体、及びＳＢＳ型スチレン－ブタジエンブロック共重合体、並びにこれらの水素添加物等が挙げられる。上記熱可塑性樹脂としては、ビニル重合体及びビニル共重合体等が挙げられる。上記熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂及びメラミン樹脂等が挙げられる。上記熱可塑性樹脂の架橋としては、ポリエチレングリコールメタクリレート、アルコキシ化トリメチロールプロパンメタクリレートやアルコキシ化ペンタエリスリトールメタクリレート等の導入が挙げられる。上記水溶性樹脂としては、ポリビニルアルコール、ポリアクリル酸、ポリアクリルアミド、ポリビニルピロリドン、ポリエチレンオキシド及びメチルセルロース等が挙げられる。また、重合度の調整に、連鎖移動剤を使用してもよい。連鎖移動剤としては、チオールや四塩化炭素等が挙げられる。 Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polydodecyl (meth) acrylate, and polystearyl (meth) acrylate. Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. Examples of the crosslinking of the thermoplastic resin include introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate and the like. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Moreover, you may use a chain transfer agent for adjustment of a polymerization degree. Examples of the chain transfer agent include thiol and carbon tetrachloride.
　上記導電部の表面上に絶縁性物質を配置する方法としては、化学的方法、及び物理的もしくは機械的方法等が挙げられる。上記化学的方法としては、例えば、界面重合法、粒子存在下での懸濁重合法及び乳化重合法等が挙げられる。上記物理的もしくは機械的方法としては、スプレードライ、ハイブリダイゼーション、静電付着法、噴霧法、ディッピング及び真空蒸着による方法等が挙げられる。絶縁性物質が脱離し難いことから、上記導電部の表面に、化学結合を介して上記絶縁性物質を配置する方法が好ましい。 As a method of disposing an insulating substance on the surface of the conductive part, there are a chemical method, a physical or mechanical method, and the like. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. A method of disposing the insulating substance on the surface of the conductive part via a chemical bond is preferable because the insulating substance is difficult to be detached.
　上記導電部の外表面、及び絶縁性物質の表面はそれぞれ、反応性官能基を有する化合物によって被覆されていてもよい。導電部の外表面と絶縁性物質の表面とは、直接化学結合していなくてもよく、反応性官能基を有する化合物によって間接的に化学結合していてもよい。導電部の外表面にカルボキシル基を導入した後、該カルボキシル基がポリエチレンイミン等の高分子電解質を介して絶縁性物質の表面の官能基と化学結合していても構わない。 The outer surface of the conductive part and the surface of the insulating substance may each be coated with a compound having a reactive functional group. The outer surface of the conductive part and the surface of the insulating substance may not be directly chemically bonded, but may be indirectly chemically bonded by a compound having a reactive functional group. After introducing a carboxyl group into the outer surface of the conductive part, the carboxyl group may be chemically bonded to a functional group on the surface of the insulating substance via a polymer electrolyte such as polyethyleneimine.
　（導電材料）
　本発明に係る導電材料は、上述した導電性粒子と、バインダーとを含む。上記導電性粒子は、バインダー中に分散されて用いられることが好ましく、バインダー中に分散されて導電材料として用いられることが好ましい。上記導電材料は、異方性導電材料であることが好ましい。上記導電材料は、電極間の電気的な接続に用いられることが好ましい。上記導電材料は回路接続用導電材料であることが好ましい。 (Conductive material)
The conductive material according to the present invention includes the above-described conductive particles and a binder. The conductive particles are preferably used by being dispersed in a binder, and are preferably used as a conductive material by being dispersed in a binder. The conductive material is preferably an anisotropic conductive material. The conductive material is preferably used for electrical connection between electrodes. The conductive material is preferably a conductive material for circuit connection.
　上記バインダーは特に限定されない。上記バインダーとして、公知の絶縁性の樹脂が用いられる。上記バインダーは、熱可塑性成分（熱可塑性化合物）又は硬化性成分を含むことが好ましく、硬化性成分を含むことがより好ましい。上記硬化性成分としては、光硬化性成分及び熱硬化性成分が挙げられる。上記光硬化性成分は、光硬化性化合物及び光重合開始剤を含むことが好ましい。上記熱硬化性成分は、熱硬化性化合物及び熱硬化剤を含むことが好ましい。 The above binder is not particularly limited. A known insulating resin is used as the binder. The binder preferably includes a thermoplastic component (thermoplastic compound) or a curable component, and more preferably includes a curable component. Examples of the curable component include a photocurable component and a thermosetting component. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator. The thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
　上記バインダーとしては、ビニル樹脂、熱可塑性樹脂、硬化性樹脂、熱可塑性ブロック共重合体及びエラストマー等が挙げられる。上記バインダーは１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the binder include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder, only 1 type may be used and 2 or more types may be used together.
　上記ビニル樹脂としては、例えば、酢酸ビニル樹脂、アクリル樹脂及びスチレン樹脂等が挙げられる。上記熱可塑性樹脂としては、例えば、ポリオレフィン樹脂、エチレン－酢酸ビニル共重合体及びポリアミド樹脂等が挙げられる。上記硬化性樹脂としては、例えば、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂及び不飽和ポリエステル樹脂等が挙げられる。なお、上記硬化性樹脂は、常温硬化型樹脂、熱硬化型樹脂、光硬化型樹脂又は湿気硬化型樹脂であってもよい。上記硬化性樹脂は、硬化剤と併用されてもよい。上記熱可塑性ブロック共重合体としては、例えば、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物、及びスチレン－イソプレン－スチレンブロック共重合体の水素添加物等が挙げられる。上記エラストマーとしては、例えば、スチレン－ブタジエン共重合ゴム、及びアクリロニトリル－スチレンブロック共重合ゴム等が挙げられる。 Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin. Examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
　上記導電材料は、上記導電性粒子及び上記バインダーの他に、例えば、充填剤、増量剤、軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤及び難燃剤等の各種添加剤を含んでいてもよい。 In addition to the conductive particles and the binder, the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer. In addition, various additives such as ultraviolet absorbers, lubricants, antistatic agents and flame retardants may be contained.
　上記バインダー中に上記導電性粒子を分散させる方法は、従来公知の分散方法を用いることができ、特に限定されない。上記バインダー中に上記導電性粒子を分散させる方法としては、上記バインダー中に上記導電性粒子を添加した後、プラネタリーミキサー等で混練して分散させる方法、上記導電性粒子を水又は有機溶剤中にホモジナイザー等を用いて均一に分散させた後、上記バインダー中に添加し、プラネタリーミキサー等で混練して分散させる方法が挙げられる。さらに、上記バインダー中に上記導電性粒子を分散させる方法としては、上記バインダーを水又は有機溶剤等で希釈した後、上記導電性粒子を添加し、プラネタリーミキサー等で混練して分散させる方法等が挙げられる。 The method for dispersing the conductive particles in the binder is not particularly limited, and a conventionally known dispersion method can be used. As a method for dispersing the conductive particles in the binder, after adding the conductive particles in the binder, a method of kneading and dispersing with a planetary mixer or the like, the conductive particles in water or an organic solvent And a homogenizer or the like, and then added to the binder and kneaded and dispersed by a planetary mixer or the like. Furthermore, as a method of dispersing the conductive particles in the binder, after the binder is diluted with water or an organic solvent, the conductive particles are added, and kneaded and dispersed by a planetary mixer or the like. Is mentioned.
　上記導電材料は、導電ペースト及び導電フィルム等として使用され得る。上記導電材料が、導電フィルムである場合には、導電性粒子を含む導電フィルムに、導電性粒子を含まないフィルムが積層されていてもよい。上記導電ペーストは、異方性導電ペーストであることが好ましい。上記導電フィルムは、異方性導電フィルムであることが好ましい。 The conductive material can be used as a conductive paste and a conductive film. When the conductive material is a conductive film, a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.
　上記導電材料１００重量％中、上記バインダーの含有量は、好ましくは１０重量％以上、より好ましくは３０重量％以上、さらに好ましくは５０重量％以上、特に好ましくは７０重量％以上であり、好ましくは９９．９９重量％以下、より好ましくは９９．９重量％以下である。上記バインダーの含有量が、上記下限以上及び上記上限以下であると、電極間に導電性粒子が効率的に配置され、導電材料により接続された接続対象部材の接続信頼性がより一層高くなる。 The content of the binder in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, and particularly preferably 70% by weight or more, preferably It is 99.99 weight% or less, More preferably, it is 99.9 weight% or less. When the content of the binder is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.
　上記導電材料１００重量％中、上記導電性粒子の含有量は、好ましくは０．０１重量％以上、より好ましくは０．１重量％以上であり、好ましくは８０重量％以下、より好ましくは６０重量％以下、さらに好ましくは４０重量％以下、特に好ましくは２０重量％以下、最も好ましくは１０重量％以下である。上記導電性粒子の含有量が、上記下限以上及び上記上限以下であると、電極間の導通信頼性がより一層高くなる。 The content of the conductive particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. % Or less, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.
　（接着剤）
　本発明に係る接着剤は、上述した樹脂粒子と、バインダーとを含む。上記樹脂粒子は、バインダー中に分散されて用いられることが好ましく、バインダー中に分散されて接着剤として用いられることが好ましい。上記樹脂粒子は、バインダー中でスペーサとして用いられることが好ましい。上記接着剤は、導電性粒子を含んでいなくてもよい。 (adhesive)
The adhesive according to the present invention includes the resin particles described above and a binder. The resin particles are preferably used by being dispersed in a binder, and are preferably used as an adhesive by being dispersed in a binder. The resin particles are preferably used as a spacer in the binder. The adhesive may not contain conductive particles.
　上記接着剤は、２つの接続対象部材を接着する接着層を形成するために用いられる。さらに、上記接着剤は、上記接着層のギャップを高精度に制御するため、又は上記接着層の応力を緩和するため等に用いられる。 The adhesive is used to form an adhesive layer that adheres two connection target members. Further, the adhesive is used for controlling the gap of the adhesive layer with high accuracy, or for relaxing the stress of the adhesive layer.
　上記バインダーは特に限定されない。上記バインダーの具体例としては、上述した導電材料に用いられるバインダー等が挙げられる。上記接着剤は、上記バインダーとして、エポキシ樹脂を含むことが好ましい。 The above binder is not particularly limited. Specific examples of the binder include binders used for the above-described conductive materials. The adhesive preferably contains an epoxy resin as the binder.
　上記接着剤１００重量％中、上記バインダーの含有量は、好ましくは１０重量％以上、より好ましくは３０重量％以上、さらに好ましくは５０重量％以上、特に好ましくは７０重量％以上であり、好ましくは９９．９９重量％以下、より好ましくは９９．９重量％以下である。上記バインダーの含有量が、上記下限以上及び上記上限以下であると、上記接着層の接着力をより一層効果的に高めることができ、上記樹脂粒子がスペーサとしての機能をより一層効果的に発揮することができる。 The content of the binder in 100% by weight of the adhesive is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably It is 99.99 weight% or less, More preferably, it is 99.9 weight% or less. When the content of the binder is not less than the above lower limit and not more than the above upper limit, the adhesive force of the adhesive layer can be further effectively increased, and the resin particles can more effectively exhibit the function as a spacer. can do.
　上記接着剤１００重量％中、上記樹脂粒子の含有量は、好ましくは０．０１重量％以上、より好ましくは０．１重量％以上であり、好ましくは８０重量％以下、より好ましくは６０重量％以下、さらに好ましくは４０重量％以下、特に好ましくは２０重量％以下、最も好ましくは１０重量％以下である。上記樹脂粒子の含有量が、上記下限以上及び上記上限以下であると、上記樹脂粒子がスペーサとしての機能をより一層効果的に発揮することができる。 The content of the resin particles in 100% by weight of the adhesive is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. Hereinafter, it is more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less. When the content of the resin particles is not less than the above lower limit and not more than the above upper limit, the resin particles can more effectively exhibit the function as a spacer.
　（接続構造体）
　上記導電性粒子を用いて、又は上記導電性粒子とバインダーとを含む導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。 (Connection structure)
A connection structure can be obtained by connecting the connection target members using the conductive particles or using a conductive material containing the conductive particles and a binder.
　本発明に係る接続構造体は、第１の電極を表面に有する第１の接続対象部材と、第２の電極を表面に有する第２の接続対象部材と、上記第１の接続対象部材と、上記第２の接続対象部材とを接続している接続部とを備える。上記接続部の材料が、上述した樹脂粒子を含む。上記接続部の材料が、上述した導電性粒子であるか、又は上述した導電材料であることが好ましい。上記接続部が、上述した導電性粒子により形成されているか、又は上述した導電材料により形成されている接続構造体であることが好ましい。 The connection structure according to the present invention includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connecting portion connecting the second connection target member. The material of the connection part includes the resin particles described above. It is preferable that the material of the connection portion is the above-described conductive particles or the above-described conductive material. It is preferable that the connection portion is formed of the above-described conductive particles or a connection structure formed of the above-described conductive material.
　上記導電性粒子が単独で用いられた場合には、接続部自体が導電性粒子である。すなわち、第１，第２の接続対象部材が上記導電性粒子により接続される。上記接続構造体を得るために用いられる上記導電材料は、異方性導電材料であることが好ましい。上記第１の電極と上記第２の電極とが、上記接続部により電気的に接続されていることが好ましい。 When the conductive particles are used alone, the connection part itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles. The conductive material used for obtaining the connection structure is preferably an anisotropic conductive material. It is preferable that the first electrode and the second electrode are electrically connected by the connecting portion.
　図４は、図１に示す導電性粒子１を用いた接続構造体の一例を示す断面図である。 FIG. 4 is a cross-sectional view showing an example of a connection structure using the conductive particles 1 shown in FIG.
　図４に示す接続構造体４１は、第１の接続対象部材４２と、第２の接続対象部材４３と、第１の接続対象部材４２と第２の接続対象部材４３とを接続している接続部４４とを備える。接続部４４は、導電性粒子１とバインダーとを含む導電材料により形成されている。図４では、図示の便宜上、導電性粒子１は略図的に示されている。導電性粒子１に代えて、導電性粒子２１，３１等の他の導電性粒子を用いてもよい。 The connection structure 41 shown in FIG. 4 is a connection that connects the first connection target member 42, the second connection target member 43, and the first connection target member 42 and the second connection target member 43. Part 44. The connection part 44 is formed of a conductive material including the conductive particles 1 and a binder. In FIG. 4, the conductive particles 1 are schematically shown for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 21 and 31 may be used.
　第１の接続対象部材４２は表面（上面）に、複数の第１の電極４２ａを有する。第２の接続対象部材４３は表面（下面）に、複数の第２の電極４３ａを有する。第１の電極４２ａと第２の電極４３ａとが、１つ又は複数の導電性粒子１により電気的に接続されている。従って、第１，第２の接続対象部材４２，４３が導電性粒子１により電気的に接続されている。 The first connection target member 42 has a plurality of first electrodes 42a on the surface (upper surface). The second connection target member 43 has a plurality of second electrodes 43a on the surface (lower surface). The first electrode 42 a and the second electrode 43 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 42 and 43 are electrically connected by the conductive particles 1.
　図５は、本発明に係る樹脂粒子を用いた接続構造体の一例を示す断面図である。 FIG. 5 is a cross-sectional view showing an example of a connection structure using the resin particles according to the present invention.
　図５に示す接続構造体５１は、第１の接続対象部材５２と、第２の接続対象部材５３と、第１の接続対象部材５２と第２の接続対象部材５３とを接着している接着層５４とを備える。 The connection structure 51 shown in FIG. 5 is an adhesive that bonds the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53. Layer 54.
　接着層５４は、上述した樹脂粒子１１を含む。樹脂粒子１１は、第１，第２の接続対象部材５２，５３の双方に接していない。樹脂粒子１１は、応力緩和用スペーサとして用いられている。 The adhesive layer 54 includes the resin particles 11 described above. The resin particles 11 are not in contact with both the first and second connection target members 52 and 53. The resin particles 11 are used as stress relaxation spacers.
　接着層５４は、ギャップ制御粒子６１と、熱硬化性成分６２とを含む。接着層５４では、ギャップ制御粒子６１が、第１，第２の接続対象部材５２，５３の双方に接している。ギャップ制御粒子６１は導電性粒子であってもよく、導電性を有さない粒子であってもよい。上記ギャップ制御粒子は、上述した樹脂粒子であってもよい。熱硬化性成分６２は、熱硬化性化合物と熱硬化剤とを含む。熱硬化性成分６２は、熱硬化性化合物の硬化物である。熱硬化性成分６２は、熱硬化性化合物を硬化させることにより形成されている。 The adhesive layer 54 includes gap control particles 61 and a thermosetting component 62. In the adhesive layer 54, the gap control particles 61 are in contact with both the first and second connection target members 52 and 53. The gap control particles 61 may be conductive particles or non-conductive particles. The gap control particles may be the resin particles described above. The thermosetting component 62 includes a thermosetting compound and a thermosetting agent. The thermosetting component 62 is a cured product of a thermosetting compound. The thermosetting component 62 is formed by curing a thermosetting compound.
　上記第１の接続対象部材は、第１の電極を表面に有していてもよい。上記第２の接続対象部材は、第２の電極を表面に有していてもよい。 The first connection object member may have a first electrode on the surface. The second connection target member may have a second electrode on the surface.
　上記接続構造体の製造方法は特に限定されない。接続構造体の製造方法の一例として、第１の接続対象部材と第２の接続対象部材との間に上記導電材料を配置し、積層体を得た後、該積層体を加熱及び加圧する方法等が挙げられる。上記加圧時の圧力は９．８×１０４Ｐａ～４．９×１０６Ｐａ程度である。上記加熱時の温度は、１２０℃～２２０℃程度である。フレキシブルプリント基板の電極、樹脂フィルム上に配置された電極及びタッチパネルの電極を接続するための上記加圧時の圧力は９．８×１０４Ｐａ～１．０×１０６Ｐａ程度である。 The manufacturing method of the connection structure is not particularly limited. As an example of a method of manufacturing a connection structure, a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc. The pressure at the time of pressurization is about 9.8 × 10 4 Pa to 4.9 × 10 6 Pa. The temperature during the heating is about 120 ° C. to 220 ° C. The pressure at the time of pressurization for connecting the electrode of the flexible printed board, the electrode arranged on the resin film, and the electrode of the touch panel is about 9.8 × 10 4 Pa to 1.0 × 10 6 Pa.
　上記接続対象部材としては、具体的には、半導体チップ、コンデンサ及びダイオード等の電子部品、並びにプリント基板、フレキシブルプリント基板、ガラスエポキシ基板及びガラス基板等の回路基板等の電子部品等が挙げられる。上記接続対象部材は電子部品であることが好ましい。上記第１の接続対象部材及び上記第２の接続対象部材の内の少なくとも一方は、半導体ウェハ又は半導体チップであることが好ましい。上記接続構造体は、半導体装置であることが好ましい。 Specific examples of the connection target member include electronic components such as a semiconductor chip, a capacitor, and a diode, and electronic components such as a circuit board such as a printed board, a flexible printed board, a glass epoxy board, and a glass board. The connection target member is preferably an electronic component. At least one of the first connection target member and the second connection target member is preferably a semiconductor wafer or a semiconductor chip. The connection structure is preferably a semiconductor device.
　上記導電材料は、電子部品を接続するための導電材料であることが好ましい。上記導電ペーストはペースト状の導電材料であり、ペースト状の状態で接続対象部材上に塗工されることが好ましい。 The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in a paste-like state.
　上記導電性粒子、上記導電材料及び上記接着剤は、タッチパネルにも好適に用いられる。従って、上記接続対象部材は、フレキシブル基板であるか、又は樹脂フィルムの表面上に電極が配置された接続対象部材であることも好ましい。上記接続対象部材は、フレキシブル基板であることが好ましく、樹脂フィルムの表面上に電極が配置された接続対象部材であることが好ましい。上記フレキシブル基板がフレキシブルプリント基板等である場合に、フレキシブル基板は一般に電極を表面に有する。 The conductive particles, the conductive material, and the adhesive are also suitably used for touch panels. Therefore, the connection target member is preferably a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film. The connection target member is preferably a flexible substrate, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film. When the flexible substrate is a flexible printed substrate or the like, the flexible substrate generally has electrodes on the surface.
　上記接続対象部材に設けられている電極としては、金電極、ニッケル電極、錫電極、アルミニウム電極、銀電極、ＳＵＳ電極、銅電極、モリブデン電極及びタングステン電極等の金属電極が挙げられる。上記接続対象部材がフレキシブルプリント基板である場合には、上記電極は金電極、ニッケル電極、錫電極又は銅電極であることが好ましい。上記接続対象部材がガラス基板である場合には、上記電極はアルミニウム電極、銅電極、モリブデン電極又はタングステン電極であることが好ましい。なお、上記電極がアルミニウム電極である場合には、アルミニウムのみで形成された電極であってもよく、金属酸化物層の表面にアルミニウム層が積層された電極であってもよい。上記金属酸化物層の材料としては、３価の金属元素がドープされた酸化インジウム及び３価の金属元素がドープされた酸化亜鉛等が挙げられる。上記３価の金属元素としては、Ｓｎ、Ａｌ及びＧａ等が挙げられる。 Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a silver electrode, a SUS electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode. When the connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.
　（液晶表示素子）
　上記樹脂粒子は、液晶表示素子用スペーサとして好適に用いることができる。 (Liquid crystal display element)
The resin particles can be suitably used as a spacer for a liquid crystal display element.
　本発明に係る液晶表示素子は、第１の液晶表示素子用部材と、第２の液晶表示素子用部材と、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材との間に配置されたスペーサとを備える。上記スペーサは、上述した樹脂粒子である。 The liquid crystal display element according to the present invention includes a first liquid crystal display element member, a second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member. And a spacer disposed therebetween. The spacer is the resin particle described above.
　上記液晶表示素子は、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材とが対向した状態で、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材との外周をシールしているシール部を備えていてもよい。 The liquid crystal display element has the first liquid crystal display element member and the second liquid crystal display element member in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other. You may provide the seal | sticker part which is sealing the outer periphery with a member.
　上記樹脂粒子は、液晶表示素子用周辺シール剤に用いることもできる。液晶表示素子は、第１の液晶表示素子用部材と、第２の液晶表示素子用部材と、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材とが対向した状態で、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材との外周をシールしているシール部を備える。液晶表示素子は、上記シール部の内側で、上記第１の液晶表示素子用部材と上記第２の液晶表示素子用部材との間に配置されている液晶を備える。この液晶表示素子では、液晶滴下工法が適用され、かつ上記シール部が、液晶滴下工法用シール剤を熱硬化させることにより形成されている。 The resin particles can also be used as a peripheral sealing agent for liquid crystal display elements. In the liquid crystal display element, the first liquid crystal display element member, the second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member face each other. And a seal portion that seals the outer periphery of the first liquid crystal display element member and the second liquid crystal display element member. The liquid crystal display element includes a liquid crystal disposed between the first liquid crystal display element member and the second liquid crystal display element member inside the seal portion. In this liquid crystal display element, a liquid crystal dropping method is applied, and the seal portion is formed by thermosetting a sealing agent for a liquid crystal dropping method.
　図６は、本発明に係る樹脂粒子を液晶表示素子用スペーサとして用いた液晶表示素子の一例を示す断面図である。 FIG. 6 is a cross-sectional view showing an example of a liquid crystal display element using the resin particles according to the present invention as a spacer for a liquid crystal display element.
　図６に示す液晶表示素子８１は、一対の透明ガラス基板８２を有する。透明ガラス基板８２は、対向する面に絶縁膜（図示せず）を有する。絶縁膜の材料としては、例えば、ＳｉＯ２等が挙げられる。透明ガラス基板８２における絶縁膜上に透明電極８３が形成されている。透明電極８３の材料としては、ＩＴＯ等が挙げられる。透明電極８３は、例えば、フォトリソグラフィーによりパターニングして形成可能である。透明ガラス基板８２の表面上の透明電極８３上に、配向膜８４が形成されている。配向膜８４の材料としては、ポリイミド等が挙げられる。 A liquid crystal display element 81 illustrated in FIG. 6 includes a pair of transparent glass substrates 82. The transparent glass substrate 82 has an insulating film (not shown) on the opposing surface. Examples of the material for the insulating film include SiO 2 . A transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. Examples of the material of the transparent electrode 83 include ITO. The transparent electrode 83 can be formed by patterning, for example, by photolithography. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. Examples of the material of the alignment film 84 include polyimide.
　一対の透明ガラス基板８２間には、液晶８５が封入されている。一対の透明ガラス基板８２間には、複数の樹脂粒子１１が配置されている。樹脂粒子１１は、液晶表示素子用スペーサとして用いられている。複数の樹脂粒子１１により、一対の透明ガラス基板８２の間隔が規制されている。一対の透明ガラス基板８２の縁部間には、シール剤８６が配置されている。シール剤８６によって、液晶８５の外部への流出が防がれている。シール剤８６には、樹脂粒子１１と粒径のみが異なる樹脂粒子１１Ａが含まれている。 A liquid crystal 85 is sealed between the pair of transparent glass substrates 82. A plurality of resin particles 11 are disposed between the pair of transparent glass substrates 82. The resin particle 11 is used as a spacer for a liquid crystal display element. The interval between the pair of transparent glass substrates 82 is regulated by the plurality of resin particles 11. A sealing agent 86 is disposed between the edges of the pair of transparent glass substrates 82. Outflow of the liquid crystal 85 to the outside is prevented by the sealing agent 86. The sealing agent 86 includes resin particles 11A that differ from the resin particles 11 only in particle diameter.
　上記液晶表示素子において１ｍｍ２あたりの液晶表示素子用スペーサの配置密度は、好ましくは１０個／ｍｍ２以上であり、好ましくは１０００個／ｍｍ２以下である。上記配置密度が１０個／ｍｍ２以上であると、セルギャップがより一層均一になる。上記配置密度が１０００個／ｍｍ２以下であると、液晶表示素子のコントラストがより一層良好になる。 In the liquid crystal display element, the arrangement density of spacers for liquid crystal display elements per 1 mm 2 is preferably 10 pieces / mm 2 or more, and preferably 1000 pieces / mm 2 or less. When the arrangement density is 10 pieces / mm 2 or more, the cell gap becomes even more uniform. When the arrangement density is 1000 / mm 2 or less, the contrast of the liquid crystal display element is further improved.
　以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.
　（実施例１）
　（１）樹脂粒子の作製
　種粒子として平均粒子径６．０μｍのポリスチレン粒子を用意した。上記ポリスチレン粒子５．０重量部と、イオン交換水９００重量部と、ポリビニルアルコールの５重量％水溶液１７０重量部とを混合し、混合液を調製した。上記混合液を超音波により分散させた後、セパラブルフラスコに入れて、均一に撹拌した。 (Example 1)
(1) Production of resin particles Polystyrene particles having an average particle diameter of 6.0 μm were prepared as seed particles. 5.0 parts by weight of the polystyrene particles, 900 parts by weight of ion-exchanged water, and 170 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol were mixed to prepare a mixed solution. After the above mixed solution was dispersed by ultrasonic waves, it was put into a separable flask and stirred uniformly.
　また、重合性官能基を１個有し、かつ環状有機基を有する第１の重合性化合物１としてメタクリル酸シクロヘキシルを用意し、重合性官能基を１個有し、かつ環状有機基を有する第１の重合性化合物２としてイソボルニルアクリレートを用意した。また、重合性官能基を２個以上有し、かつ環状有機基を有する第２の重合性化合物としてジビニルベンゼンを用意した。 Further, cyclohexyl methacrylate is prepared as the first polymerizable compound 1 having one polymerizable functional group and having a cyclic organic group, and having a polymerizable functional group and having a cyclic organic group. Isobornyl acrylate was prepared as 1 polymerizable compound 2. Further, divinylbenzene was prepared as a second polymerizable compound having two or more polymerizable functional groups and having a cyclic organic group.
　次に、ポリテトラメチレングリコールジアクリレート９重量部と、ジビニルベンゼン１重量部と、メタクリル酸シクロヘキシル１５重量部と、イソボルニルアクリレート７５重量部とを混合し、混合物を得た。得られた混合物に、過酸化ベンゾイル（日油社製「ナイパーＢＷ」）６．０重量部を添加し、さらに、イオン交換水１０００重量部を添加し、乳化液を調製した。 Next, 9 parts by weight of polytetramethylene glycol diacrylate, 1 part by weight of divinylbenzene, 15 parts by weight of cyclohexyl methacrylate and 75 parts by weight of isobornyl acrylate were mixed to obtain a mixture. To the obtained mixture, 6.0 parts by weight of benzoyl peroxide (“NIPER BW” manufactured by NOF Corporation) was added, and further 1000 parts by weight of ion-exchanged water was added to prepare an emulsion.
　セパラブルフラスコ中の上記混合液に、上記乳化液をさらに添加し、１６時間撹拌し、種粒子にモノマーを吸収させて、モノマーが膨潤した種粒子を含む懸濁液を得た。 The emulsion was further added to the mixed solution in the separable flask and stirred for 16 hours to absorb the monomer in the seed particles, thereby obtaining a suspension containing seed particles in which the monomer was swollen.
　その後、ポリビニルアルコールの５重量％水溶液５１０重量部を添加し、加熱を開始して８５℃で１０時間反応させ、樹脂粒子を得た。 Thereafter, 510 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol was added, heating was started, and reaction was performed at 85 ° C. for 10 hours to obtain resin particles.
　（２）導電性粒子の作製
　得られた樹脂粒子を洗浄し、分級操作を行った後に乾燥した。その後、無電解めっき法により、得られた樹脂粒子の表面に、ニッケル層を形成し、導電性粒子を作製した。なお、ニッケル層の厚さは、０．１μｍであった。 (2) Production of conductive particles The obtained resin particles were washed, classified and dried. Thereafter, a nickel layer was formed on the surface of the obtained resin particles by electroless plating to produce conductive particles. The thickness of the nickel layer was 0.1 μm.
　（３）導電材料（異方性導電ペースト）の作製
　導電材料（異方性導電ペースト）を作製するため、以下の材料を用意した。 (3) Production of conductive material (anisotropic conductive paste) The following materials were prepared to produce a conductive material (anisotropic conductive paste).
　（導電材料（異方性導電ペースト）の材料）
　熱硬化性化合物Ａ：エポキシ化合物（ナガセケムテックス社製「ＥＰ－３３００Ｐ」）
　熱硬化性化合物Ｂ：エポキシ化合物（ＤＩＣ社製「ＥＰＩＣＬＯＮ　ＨＰ－４０３２Ｄ」）
　熱硬化性化合物Ｃ：エポキシ化合物（四日市合成社製「エポゴーセーＰＴ」、ポリテトラメチレングリコールジグリシジルエーテル）
　熱硬化剤：熱カチオン発生剤（三新化学社製　サンエイド「ＳＩ－６０」）
　フィラー：シリカ（平均粒子径０．２５μｍ） (Material of conductive material (anisotropic conductive paste))
Thermosetting compound A: Epoxy compound (“EP-3300P” manufactured by Nagase ChemteX Corporation)
Thermosetting compound B: Epoxy compound (“EPICLON HP-4032D” manufactured by DIC)
Thermosetting compound C: Epoxy compound (“Epogosei PT”, polytetramethylene glycol diglycidyl ether, manufactured by Yokkaichi Gosei Co., Ltd.)
Thermosetting agent: Thermal cation generator (Sun Shin “SI-60” manufactured by Sanshin Chemical Co., Ltd.)
Filler: Silica (average particle size 0.25 μm)
　導電材料（異方性導電ペースト）を以下のようにして作製した。 A conductive material (anisotropic conductive paste) was produced as follows.
　（導電材料（異方性導電ペースト）の作製方法）
　熱硬化性化合物Ａ１０重量部と、熱硬化性化合物Ｂ１０重量部と、熱硬化性化合物Ｃ１５重量部と、熱硬化剤５重量部と、フィラー２０重量部とを配合し、配合物を得た。さらに得られた導電性粒子を配合物１００重量％中での含有量が１０重量％となるように添加した後、遊星式攪拌機を用いて２０００ｒｐｍで５分間攪拌することにより、導電材料（異方性導電ペースト）を得た。 (Method for producing conductive material (anisotropic conductive paste))
10 parts by weight of thermosetting compound A, 10 parts by weight of thermosetting compound B, 15 parts by weight of thermosetting compound C, 5 parts by weight of thermosetting agent, and 20 parts by weight of filler were blended to obtain a blend. Furthermore, after adding the obtained electroconductive particle so that content in 100 weight% of compounds may be 10 weight%, it stirs at 2000 rpm for 5 minutes using a planetary stirrer, and conductive material (anisotropic) Conductive paste) was obtained.
　（４）接続構造体の作製
　第１の接続対象部材として、Ｌ／Ｓが２０μｍ／２０μｍのアルミニウム電極パターンを上面に有するガラス基板を用意した。また、第２の接続対象部材として、Ｌ／Ｓが２０μｍ／２０μｍの金電極パターン（金電極厚み２０μｍ）を下面に有する半導体チップを用意した。 (4) Production of connection structure As a first connection target member, a glass substrate having an aluminum electrode pattern with an L / S of 20 μm / 20 μm on the upper surface was prepared. As a second connection target member, a semiconductor chip having a gold electrode pattern (gold electrode thickness: 20 μm) with L / S of 20 μm / 20 μm on the lower surface was prepared.
　上記ガラス基板の上面に、作製直後の導電材料（異方性導電ペースト）を厚さ３０μｍとなるように塗工し、導電材料（異方性導電ペースト）層を形成した。次に、導電材料（異方性導電ペースト）層の上面に上記半導体チップを、電極同士が対向するように積層した。その後、導電材料（異方性導電ペースト）層の温度が１７０℃となるようにヘッドの温度を調整しながら、半導体チップの上面に加圧加熱ヘッドを載せ、導電材料（異方性導電ペースト）層を１７０℃、１．０ＭＰａ、及び１５秒間の条件で硬化させ、接続構造体を得た。 The conductive material (anisotropic conductive paste) immediately after fabrication was applied to the upper surface of the glass substrate so as to have a thickness of 30 μm to form a conductive material (anisotropic conductive paste) layer. Next, the semiconductor chip was stacked on the upper surface of the conductive material (anisotropic conductive paste) layer so that the electrodes face each other. Then, while adjusting the head temperature so that the temperature of the conductive material (anisotropic conductive paste) layer becomes 170 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip, and the conductive material (anisotropic conductive paste) The layer was cured under the conditions of 170 ° C., 1.0 MPa, and 15 seconds to obtain a connection structure.
　（実施例２）
　樹脂粒子を作製する際に、ポリテトラメチレングリコールジアクリレート９重量部をメタクリル酸メチル９１重量部に変更し、メタクリル酸シクロヘキシルの配合量を１５重量部から５重量部に変更し、イソボルニルアクリレートの配合量を７５重量部から３重量部に変更した。上記の変更以外は、実施例１と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Example 2)
When preparing resin particles, 9 parts by weight of polytetramethylene glycol diacrylate was changed to 91 parts by weight of methyl methacrylate, the amount of cyclohexyl methacrylate was changed from 15 parts by weight to 5 parts by weight, and isobornyl acrylate Was changed from 75 parts by weight to 3 parts by weight. Except for the above change, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1.
　（実施例３）
　樹脂粒子を作製する際に、ポリテトラメチレングリコールジアクリレート９重量部を２－メタクロイロキシエチルアシッドホスフェート９重量部に変更したこと以外は、実施例１と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Example 3)
In the same manner as in Example 1, except that 9 parts by weight of polytetramethylene glycol diacrylate was changed to 9 parts by weight of 2-methacryloxyethyl acid phosphate when preparing the resin particles, the conductive particles and the conductive material were used. And the connection structure was obtained.
　（実施例４）
　樹脂粒子を作製する際に、メタクリル酸シクロヘキシル５重量部をフェノキシエチレングリコールメタクリレート５重量部に変更したこと以外は、実施例２と同様にして、導電性粒子、導電材料及び接続構造体を得た。 Example 4
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 2 except that 5 parts by weight of cyclohexyl methacrylate was changed to 5 parts by weight of phenoxyethylene glycol methacrylate when producing the resin particles. .
　（実施例５）
　樹脂粒子を作製する際に、メタクリル酸シクロヘキシル５重量部をジシクロペンテニルアクリレート５重量部に変更したこと以外は、実施例２と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Example 5)
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in Example 2 except that 5 parts by weight of cyclohexyl methacrylate was changed to 5 parts by weight of dicyclopentenyl acrylate when producing the resin particles. .
　（実施例６）
　樹脂粒子を作製する際に、ジビニルベンゼン１重量部をトリシクロデカンジメタノールジアクリレート１重量部に変更したこと以外は、実施例１と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Example 6)
The conductive particles, the conductive material, and the connection structure were prepared in the same manner as in Example 1 except that 1 part by weight of divinylbenzene was changed to 1 part by weight of tricyclodecane dimethanol diacrylate when the resin particles were produced. Obtained.
　（比較例１）
　樹脂粒子を作製する際に、ポリテトラメチレングリコールジアクリレートの配合量を９重量部から１０重量部に変更したこと、及びジビニルベンゼンを配合しないように変更したこと以外は、実施例１と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Comparative Example 1)
Except that the amount of polytetramethylene glycol diacrylate was changed from 9 parts by weight to 10 parts by weight when the resin particles were prepared, and that no change was made so that divinylbenzene was not added, the same as in Example 1. Thus, conductive particles, a conductive material, and a connection structure were obtained.
　（比較例２）
　樹脂粒子を作製する際に、ポリテトラメチレングリコールジアクリレート９重量部をメタクリル酸メチル９４重量部に変更し、メタクリル酸シクロヘキシルの配合量を１５重量部から５重量部に変更し、イソボルニルアクリレートを配合しないように変更した。上記の変更以外は、実施例１と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Comparative Example 2)
When preparing resin particles, 9 parts by weight of polytetramethylene glycol diacrylate was changed to 94 parts by weight of methyl methacrylate, the amount of cyclohexyl methacrylate was changed from 15 parts by weight to 5 parts by weight, and isobornyl acrylate Was changed so as not to blend. Except for the above change, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1.
　（比較例３）
　樹脂粒子を作製する際に、ポリテトラメチレングリコールジアクリレートの配合量を９重量部から５０重量部に変更したこと、及びイソボルニルアクリレートの配合量を７５重量部から３４重量部に変更したこと以外は、実施例１と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Comparative Example 3)
When preparing resin particles, the amount of polytetramethylene glycol diacrylate was changed from 9 parts by weight to 50 parts by weight, and the amount of isobornyl acrylate was changed from 75 parts by weight to 34 parts by weight. Except for the above, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1.
　（比較例４）
　樹脂粒子を作製する際に、メタクリル酸シクロヘキシル１５重量部をフェノキシエチレングリコールメタクリレート１５重量部に変更したこと以外は、比較例１と同様にして、導電性粒子、導電材料及び接続構造体を得た。 (Comparative Example 4)
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in Comparative Example 1 except that 15 parts by weight of cyclohexyl methacrylate was changed to 15 parts by weight of phenoxyethylene glycol methacrylate when producing the resin particles. .
　（評価）
　（１）第１の重合性化合物に由来する構造の含有量（ＷＭ）及び第２の重合性化合物に由来する構造の含有量（ＷＤ）
　重合体を得る際に用いた第１，第２の重合性化合物の配合量及び重合後の第１，第２の重合性化合物の残存量から、重合した第１，第２の重合性化合物を求め、得られた樹脂粒子の第１の重合性化合物に由来する構造の含有量（ＷＭ）及び第２の重合性化合物に由来する構造の含有量（ＷＤ）を算出した。第１の重合性化合物に由来する構造の含有量（ＷＭ）の、第２の重合性化合物に由来する構造の含有量（ＷＤ）に対する重量比（ＷＭ／ＷＤ）を算出した。 (Evaluation)
(1) Content of structure derived from first polymerizable compound (WM) and content of structure derived from second polymerizable compound (WD)
From the blended amount of the first and second polymerizable compounds used in obtaining the polymer and the remaining amount of the first and second polymerizable compounds after polymerization, the polymerized first and second polymerizable compounds are obtained. The content (WM) derived from the first polymerizable compound and the content (WD) derived from the second polymerizable compound of the obtained resin particles were calculated. The weight ratio (WM / WD) of the content (WM) derived from the first polymerizable compound to the content (WD) derived from the second polymerizable compound was calculated.
　（２）粒子径
　得られた樹脂粒子の粒子径（加熱前の粒子径）を、粒度分布測定装置（ベックマンコールター社製「Ｍｕｌｔｉｓｉｚｅｒ４」）を用いて、約１０００００個の樹脂粒子の粒子径を測定し、平均値を算出することにより求めた。 (2) Particle size The particle size of the obtained resin particles (particle size before heating) was measured using a particle size distribution measuring device (“Multizer 4” manufactured by Beckman Coulter, Inc.). And it calculated | required by calculating an average value.
　次に、粒子径の測定に用いた樹脂粒子を１５０℃で１０００時間加熱した。１０００時間加熱後の樹脂粒子の粒子径を、上述した方法で測定した。得られた測定結果から、加熱後の樹脂粒子の粒子径の加熱前の樹脂粒子の粒子径に対する比（加熱後の樹脂粒子の粒子径／加熱前の樹脂粒子の粒子径）を算出した。 Next, the resin particles used for measurement of the particle diameter were heated at 150 ° C. for 1000 hours. The particle diameter of the resin particles after heating for 1000 hours was measured by the method described above. From the measurement results obtained, the ratio of the particle diameter of the resin particles after heating to the particle diameter of the resin particles before heating (the particle diameter of the resin particles after heating / the particle diameter of the resin particles before heating) was calculated.
　（３）１０％Ｋ値及び３０％Ｋ値
　得られた樹脂粒子の１０％Ｋ値及び３０％Ｋ値（加熱前の３０％Ｋ値）を、上述した方法で測定した。 (3) 10% K value and 30% K value The 10% K value and 30% K value (30% K value before heating) of the obtained resin particles were measured by the method described above.
　次に、３０％Ｋ値の測定に用いた樹脂粒子を１５０℃で１０００時間加熱した。１０００時間加熱後の樹脂粒子の３０％Ｋ値を、上述した方法で測定した。得られた測定結果から、加熱後の３０％Ｋ値の加熱前の３０％Ｋ値に対する比（加熱後の３０％Ｋ値／加熱前の３０％Ｋ値）を算出した。 Next, the resin particles used for the measurement of 30% K value were heated at 150 ° C. for 1000 hours. The 30% K value of the resin particles after heating for 1000 hours was measured by the method described above. From the measurement results obtained, the ratio of the 30% K value after heating to the 30% K value before heating (30% K value after heating / 30% K value before heating) was calculated.
　（４）６０％圧縮変形させた際の圧縮回復率
　得られた樹脂粒子の６０％圧縮変形させた際の圧縮回復率を、上述した方法で測定した。 (4) Compression recovery rate at 60% compression deformation The compression recovery rate at 60% compression deformation of the obtained resin particles was measured by the method described above.
　（５）めっき状態
　得られた導電性粒子を１５０℃で１０００時間加熱した。加熱後の導電性粒子の５０個のめっき状態を、走査型電子顕微鏡により観察した。めっき割れ又はめっき剥がれ等のめっきむらの有無を評価した。めっき状態を以下の基準で判定した。 (5) Plating state The obtained electroconductive particle was heated at 150 degreeC for 1000 hours. Fifty plating states of the conductive particles after heating were observed with a scanning electron microscope. The presence or absence of plating unevenness such as plating cracking or peeling off was evaluated. The plating state was determined according to the following criteria.
　［めっき状態の判定基準］
　○○：めっきむらが確認された導電性粒子が３個未満
　○：めっきむらが確認された導電性粒子が３個以上６個未満
　×：めっきむらが確認された導電性粒子が６個以上 [Criteria for plating state]
○○: Less than 3 conductive particles with uneven plating ○: 3 or more with less than 6 conductive particles with uneven plating ×: 6 or more conductive particles with uneven plating
　（６）接続強度
　マウント強度測定装置を用いて、得られた接続構造体の２６０℃での接続強度を測定した。接続強度を以下の基準で判定した。 (6) Connection strength The connection strength at 260 ° C. of the obtained connection structure was measured using a mount strength measuring device. Connection strength was determined according to the following criteria.
　［接続強度の判定基準］
　○○：シェア強度が１５０Ｎ／ｃｍ２以上
　〇：シェア強度が１００Ｎ／ｃｍ２以上１５０Ｎ／ｃｍ２未満
　×：シェア強度が１００Ｎ／ｃｍ２未満 [Connection strength criteria]
◯: Shear strength is 150 N / cm 2 or more ◯: Shear strength is 100 N / cm 2 or more and less than 150 N / cm 2 ×: Shear strength is less than 100 N / cm 2
　（７）スプリングバック
　走査型電子顕微鏡により、得られた接続構造体の接続部においてスプリングバックが発生しているか否かを観察した。スプリングバックを以下の基準で判定した。 (7) Springback With a scanning electron microscope, it was observed whether or not springback occurred at the connection portion of the obtained connection structure. Springback was determined according to the following criteria.
　［スプリングバックの判定基準］
　○：スプリングバックが発生していない
　×：スプリングバックが発生している [Springback criteria]
○: Springback has not occurred ×: Springback has occurred
　（８）冷熱サイクル特性（接続信頼性）
　得られた接続構造体を、－６５℃から１５０℃に加熱し、－６５℃に冷却する過程を１サイクルとする冷熱サイクル試験を１０００サイクル実施した。超音波探傷装置（ＳＡＴ）により、接続部において浮き又は剥離の発生の有無を観察した。冷熱サイクル特性（接続信頼性）を以下の基準で判定した。 (8) Cooling cycle characteristics (connection reliability)
The obtained connection structure was heated from −65 ° C. to 150 ° C. and cooled to −65 ° C., and a cooling cycle test was performed for 1000 cycles. With an ultrasonic flaw detector (SAT), the presence or absence of floating or peeling at the connecting portion was observed. The thermal cycle characteristics (connection reliability) were determined according to the following criteria.
　［冷熱サイクル特性（接続信頼性）の判定基準］
　○：接続部に浮き及び剥離なし
　×：接続部に浮き又は剥離がある [Criteria for cooling cycle characteristics (connection reliability)]
○: No floating or peeling at the connection part ×: There is floating or peeling at the connection part
　結果を下記の表１，２，３に示す。 The results are shown in Tables 1, 2, and 3 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（９）液晶表示素子用スペーサとしての使用例
　ＳＴＮ型液晶表示素子の作製：
　イソプロピルアルコール７０重量部と水３０重量部とを含む分散媒に、得られるスペーサ分散液１００重量％中で実施例１～６の液晶表示素子用スペーサ（樹脂粒子）を固形分濃度が２重量％となるように添加し、撹拌し、液晶表示素子用スペーサ分散液を得た。 (9) Usage example as spacer for liquid crystal display element Production of STN type liquid crystal display element:
In a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the liquid crystal display element spacers (resin particles) of Examples 1 to 6 were added at a solid content concentration of 2% by weight in 100% by weight of the resulting spacer dispersion. Was added and stirred to obtain a spacer dispersion liquid crystal display device.
　一対の透明ガラス板（縦５０ｍｍ、横５０ｍｍ、厚さ０．４ｍｍ）の一面に、ＣＶＤ法によりＳｉＯ２膜を蒸着した後、ＳｉＯ２膜の表面全体にスパッタリングによりＩＴＯ膜を形成した。得られたＩＴＯ膜付きガラス基板に、スピンコート法によりポリイミド配向膜組成物（日産化学社製、ＳＥ３５１０）を塗工し、２８０℃で９０分間焼成することによりポリイミド配向膜を形成した。配向膜にラビング処理を施した後、一方の基板の配向膜側に、液晶表示素子用スペーサを１ｍｍ２当たり１００個となるように湿式散布した。他方の基板の周辺にシール剤を形成した後、この基板とスペーサを散布した基板とをラビング方向が９０°になるように対向配置させ、両者を貼り合わせた。その後、１６０℃で９０分間処理してシール剤を硬化させて、空セル（液晶の入ってない画面）を得た。得られた空セルに、カイラル剤入りのＳＴＮ型液晶（ＤＩＣ社製）を注入し、次に注入口を封止剤で塞いだ後、１２０℃で３０分間熱処理してＳＴＮ型液晶表示素子を得た。 An SiO 2 film was deposited on one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm) by a CVD method, and then an ITO film was formed on the entire surface of the SiO 2 film by sputtering. A polyimide alignment film composition (SE3510, manufactured by Nissan Chemical Industries, Ltd.) was applied to the obtained glass substrate with an ITO film by spin coating, and baked at 280 ° C. for 90 minutes to form a polyimide alignment film. After the alignment film was rubbed, wet alignment was performed on the alignment film side of one substrate so that the number of spacers for liquid crystal display elements was 100 per 1 mm 2 . After forming a sealant around the other substrate, this substrate and the substrate on which the spacers were spread were placed opposite to each other so that the rubbing direction was 90 °, and both were bonded together. Then, it processed at 160 degreeC for 90 minute (s), the sealing agent was hardened, and the empty cell (screen which does not contain a liquid crystal) was obtained. An STN type liquid crystal containing a chiral agent (made by DIC) was injected into the obtained empty cell, and then the injection port was closed with a sealant, followed by heat treatment at 120 ° C. for 30 minutes to produce an STN type liquid crystal display element. Obtained.
　得られた液晶表示素子では、実施例１～６の液晶表示素子用スペーサ（樹脂粒子）により基板間の間隔が良好に規制されていた。また、液晶表示素子は、良好な表示品質を示した。なお、液晶表示素子の周辺シール剤に、実施例１～６の樹脂粒子を液晶表示素子用スペーサとして用いた場合でも、得られた液晶表示素子の表示品質は良好であった。 In the obtained liquid crystal display element, the distance between the substrates was well regulated by the spacers (resin particles) for liquid crystal display elements of Examples 1 to 6. Moreover, the liquid crystal display element showed favorable display quality. Even when the resin particles of Examples 1 to 6 were used as the spacer for the liquid crystal display element as the peripheral sealant of the liquid crystal display element, the display quality of the obtained liquid crystal display element was good.
　１…導電性粒子
　２…導電部
　１１…樹脂粒子
　１１Ａ…樹脂粒子
　２１…導電性粒子
　２２…導電部
　２２Ａ…第１の導電部
　２２Ｂ…第２の導電部
　３１…導電性粒子
　３１ａ…突起
　３２…導電部
　３２ａ…突起
　３３…芯物質
　３４…絶縁性物質
　４１…接続構造体
　４２…第１の接続対象部材
　４２ａ…第１の電極
　４３…第２の接続対象部材
　４３ａ…第２の電極
　４４…接続部
　５１…接続構造体
　５２…第１の接続対象部材
　５３…第２の接続対象部材
　５４…接着層
　６１…ギャップ制御粒子
　６２…熱硬化性成分
　８１…液晶表示素子
　８２…透明ガラス基板
　８３…透明電極
　８４…配向膜
　８５…液晶
　８６…シール剤 DESCRIPTION OF SYMBOLS 1 ... Conductive particle 2 ... Conductive part 11 ... Resin particle 11A ... Resin particle 21 ... Conductive particle 22 ... Conductive part 22A ... 1st conductive part 22B ... 2nd conductive part 31 ... Conductive particle 31a ... Protrusion 32 ... Conductive part 32a ... projection 33 ... core material 34 ... insulating material 41 ... connection structure 42 ... first connection object member 42a ... first electrode 43 ... second connection object member 43a ... second electrode 44 ... connection Part 51: Connection structure 52 ... First connection target member 53 ... Second connection target member 54 ... Adhesive layer 61 ... Gap control particle 62 ... Thermosetting component 81 ... Liquid crystal display element 82 ... Transparent glass substrate 83 ... Transparent Electrode 84 ... Alignment film 85 ... Liquid crystal 86 ... Sealing agent

Claims (15)

  1. 　重合性官能基を１個有し、かつ環状有機基を有する第１の重合性化合物と、重合性官能基を２個以上有し、かつ環状有機基を有する第２の重合性化合物との重合体であり、
    　前記第１の重合性化合物に由来する構造の含有量の前記第２の重合性化合物に由来する構造の含有量に対する重量比が、７以上であり、
    　樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の粒子径の加熱前の樹脂粒子の粒子径に対する比が、０．９以下である、樹脂粒子。     Weight of a first polymerizable compound having one polymerizable functional group and having a cyclic organic group and a second polymerizable compound having two or more polymerizable functional groups and having a cyclic organic group Coalesced,
    The weight ratio of the content of the structure derived from the first polymerizable compound to the content of the structure derived from the second polymerizable compound is 7 or more,
    Resin particles having a ratio of the particle diameter of the resin particles after heating to the particle diameter of the resin particles before heating of 0.9 or less when the resin particles are heated at 150 ° C. for 1000 hours.
  2. 　６０％圧縮変形させた際の圧縮回復率が、１０％以下である、請求項１に記載の樹脂粒子。 The resin particles according to claim 1, wherein a compression recovery rate when compressed and deformed by 60% is 10% or less.
  3. 　１０％Ｋ値が、３０００Ｎ／ｍｍ２以下である、請求項１又は２に記載の樹脂粒子。 The resin particle of Claim 1 or 2 whose 10% K value is 3000 N / mm < 2 > or less.
  4. 　３０％Ｋ値が、１５００Ｎ／ｍｍ２以下である、請求項１～３のいずれか１項に記載の樹脂粒子。 The resin particles according to any one of claims 1 to 3, having a 30% K value of 1500 N / mm 2 or less.
  5. 　樹脂粒子を１５０℃で１０００時間加熱したときに、加熱後の樹脂粒子の３０％Ｋ値の加熱前の樹脂粒子の３０％Ｋ値に対する比が、０．８以上１．５以下である、請求項１～４のいずれか１項に記載の樹脂粒子。 When the resin particles are heated at 150 ° C. for 1000 hours, the ratio of the 30% K value of the resin particles after heating to the 30% K value of the resin particles before heating is 0.8 or more and 1.5 or less, Item 5. The resin particle according to any one of Items 1 to 4.
  6. 　前記第１の重合性化合物における環状有機基と前記第２の重合性化合物における環状有機基とがそれぞれ、炭化水素基である、請求項１～５のいずれか１項に記載の樹脂粒子。 6. The resin particles according to claim 1, wherein the cyclic organic group in the first polymerizable compound and the cyclic organic group in the second polymerizable compound are each a hydrocarbon group.
  7. 　前記第１の重合性化合物における環状有機基が、フェニレン基、シクロヘキシル基又はイソボルニル基である、請求項１～６のいずれか１項に記載の樹脂粒子。 The resin particles according to any one of claims 1 to 6, wherein the cyclic organic group in the first polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group.
  8. 　前記第２の重合性化合物における環状有機基が、フェニレン基、シクロヘキシル基又はイソボルニル基である、請求項１～７のいずれか１項に記載の樹脂粒子。 The resin particles according to any one of claims 1 to 7, wherein the cyclic organic group in the second polymerizable compound is a phenylene group, a cyclohexyl group, or an isobornyl group.
  9. 　アシッドホスフェート化合物を含む、請求項１～８のいずれか１項に記載の樹脂粒子。 The resin particles according to any one of claims 1 to 8, comprising an acid phosphate compound.
  10. 　スペーサとして用いられるか、又は、表面上に導電部が形成され、前記導電部を有する導電性粒子を得るために用いられる、請求項１～９のいずれか１項に記載の樹脂粒子。 The resin particles according to any one of claims 1 to 9, wherein the resin particles are used as spacers or used to obtain conductive particles having a conductive part formed on a surface thereof and having the conductive part.
  11. 　請求項１～１０のいずれか１項に記載の樹脂粒子と、
    　前記樹脂粒子の表面上に配置された導電部とを備える、導電性粒子。     Resin particles according to any one of claims 1 to 10,
    Electroconductive particle provided with the electroconductive part arrange | positioned on the surface of the said resin particle.
  12. 　導電性粒子と、バインダーとを含み、
    　前記導電性粒子が、請求項１～１０のいずれか１項に記載の樹脂粒子と、前記樹脂粒子の表面上に配置された導電部とを備える、導電材料。     Containing conductive particles and a binder,
    A conductive material, wherein the conductive particles include the resin particles according to any one of claims 1 to 10 and a conductive portion disposed on a surface of the resin particles.
  13. 　請求項１～１０のいずれか１項に記載の樹脂粒子と、
    　バインダーとを含む、接着剤。     Resin particles according to any one of claims 1 to 10,
    An adhesive comprising a binder.
  14. 　第１の電極を表面に有する第１の接続対象部材と、
    　第２の電極を表面に有する第２の接続対象部材と、
    　前記第１の接続対象部材と、前記第２の接続対象部材とを接続している接続部とを備え、
    　前記接続部の材料が、請求項１～１０のいずれか１項に記載の樹脂粒子を含み、
    　前記第１の電極と前記第２の電極とが、前記接続部により電気的に接続されている、接続構造体。     A first connection object member having a first electrode on its surface;
    A second connection target member having a second electrode on its surface;
    A connecting portion connecting the first connection target member and the second connection target member;
    The material of the connecting portion includes the resin particles according to any one of claims 1 to 10,
    A connection structure in which the first electrode and the second electrode are electrically connected by the connection portion.
  15. 　第１の液晶表示素子用部材と、
    　第２の液晶表示素子用部材と、
    　前記第１の液晶表示素子用部材と前記第２の液晶表示素子用部材との間に配置されたスペーサとを備え、
    　前記スペーサが、請求項１～１０のいずれか１項に記載の樹脂粒子である、液晶表示素子。     A first liquid crystal display element member;
    A second liquid crystal display element member;
    A spacer disposed between the first liquid crystal display element member and the second liquid crystal display element member;
    A liquid crystal display element, wherein the spacer is the resin particle according to any one of claims 1 to 10.
PCT/JP2018/022071 2017-06-12 2018-06-08 Resin particles, conductive particles, conductive material, adhesive, connection structure and liquid crystal display element WO2018230470A1 (en)

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