WO2018230470A1 - 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 - Google Patents
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 Download PDFInfo
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- 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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- 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
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- 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
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- 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
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- 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
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- 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.
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Abstract
Description
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。
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
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)
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
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。
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。
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。
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。
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。
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。
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。
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。
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。
(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。
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。
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。
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)
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
(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。
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。
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。
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。
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。
○○: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
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。
○○: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
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。
○: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
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。
○: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
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。
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
Claims (15)
- 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。 - 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。 - 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。 - 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。 - 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。 - 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。
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