WO2014115468A1 - 基材粒子、導電性粒子、導電材料及び接続構造体 - Google Patents
基材粒子、導電性粒子、導電材料及び接続構造体 Download PDFInfo
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- WO2014115468A1 WO2014115468A1 PCT/JP2013/084488 JP2013084488W WO2014115468A1 WO 2014115468 A1 WO2014115468 A1 WO 2014115468A1 JP 2013084488 W JP2013084488 W JP 2013084488W WO 2014115468 A1 WO2014115468 A1 WO 2014115468A1
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Definitions
- the present invention relates to a base material particle having a conductive layer formed on the surface and used to obtain conductive particles having the conductive layer.
- the present invention also relates to a conductive particle, a conductive material, and a connection structure using the base particle.
- 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 resin.
- 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 base particles and a conductive layer disposed on the surface of the base particles may be used.
- the shell is an inorganic compound (A)
- the core is an organic polymer (b)
- the core is covered with the shell.
- Polymer particles (B) substrate particles
- Patent Document 1 also discloses conductive particles in which organic polymer particles (B) are coated with a conductive metal (C).
- Patent Document 2 discloses organic-inorganic composite particles (base particles) obtained by hydrolysis and polycondensation of a polyfunctional silane compound having a polymerizable unsaturated group in the presence of a surfactant. ) Is disclosed.
- the polyfunctional silane compound is at least one radical polymerizable group-containing first silicon compound selected from a compound represented by the following formula (X) and a derivative thereof.
- R1 represents a hydrogen atom or a methyl group
- R2 represents an optionally substituted divalent organic group having 1 to 20 carbon atoms
- R3 represents a carbon atom having 1 to 5 carbon atoms
- R 4 represents an alkyl group or a phenyl group, and R 4 represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
- Patent Document 3 discloses core-shell particles in which the surface of hard particles is covered with a soft polymer layer.
- the hard particles include metal particles such as nickel, inorganic particles such as glass fiber, alumina and silica, and resin cured particles such as cured benzoguanamine.
- Patent Document 3 describes that by providing a soft polymer layer, the contact area can be increased and the reliability can be improved.
- the distance between electrodes connected by conductive particles is narrow and the electrode area tends to be small, and there is a demand for conductive particles that can be connected with even lower resistance.
- the substrate material a relatively soft resin film substrate has been used instead of a glass substrate in order to enhance flexibility, and conductive particles that do not damage the soft substrate and the electrode are required. It is coming.
- the contact area between the electrode and the conductive particle is increased, and the conductive particle is less likely to damage the electrode.
- the binder resin between the electrodes and the conductive particles cannot be sufficiently removed when the electrodes are connected, and the resin is sandwiched between the electrodes and the conductive particles.
- the conductive layer and the oxide film on the surface of the electrode cannot be sufficiently penetrated, resulting in a problem that the connection resistance is increased. This problem occurs even when core-shell particles in which the core is covered with a shell and the shell is a relatively soft organic shell are used as the base particles.
- connection resistance may not be kept low.
- the object of the present invention is to reduce the connection resistance when the electrodes are electrically connected using conductive particles having a conductive layer formed on the surface, and the connection failure due to the occurrence of cracks in the electrodes. And it is providing the base material particle which can suppress the connection defect by springback. Moreover, the objective of this invention is providing the electroconductive particle using the said base material particle, an electroconductive material, and a connection structure.
- grains whose ratio with respect to the load value when compressing 10% of the load value of is 3 or less are provided.
- the core is an organic core and the shell is an inorganic shell.
- the thickness of the shell is 100 nm or more and 5 ⁇ m or less.
- the compression elastic modulus when the base particle is compressed by 30% is 3000 N / mm 2 or less. It is preferable that the ratio of the load value when the base material particle is compressed by 40% to the load value when the base material particle is compressed by 10% is 6 or less.
- the fracture strain of the substrate particles is preferably 10% or more and 30% or less.
- a conductive particle comprising the above-described base particle and a conductive layer disposed on the surface of the base particle.
- the conductive particle further includes an insulating substance disposed on the outer surface of the conductive layer.
- the conductive particle has a protrusion on the outer surface of the conductive layer.
- the conductive particles include conductive particles and a binder resin, and the conductive particles include the base material particles described above and a conductive layer disposed on the surface of the base material particles.
- a conductive material is provided.
- 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 and the A connection portion connecting the second connection target member, and the connection portion is formed of conductive particles or formed of a conductive material including the conductive particles and a binder resin.
- the conductive particles include the base material particles described above and a conductive layer disposed on the surface of the base material particles, and the first electrode and the second electrode are electrically connected by the conductive particles.
- a connection structure is provided which is connected in a connected manner.
- the base material particle according to the present invention is a core-shell particle including a core and a shell disposed on the surface of the core, and the base material particle according to the present invention has a compression recovery rate of less than 50%, 10% compressed compression elastic modulus when the 3000N / mm 2 or more and less than 6000 N / mm 2, since the ratio load value when compressed 10% of the load value when compressed 30% is 3 or less.
- the connection resistance can be lowered, and connection failure due to cracks in the electrodes and connection due to springback Defects can be 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 front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
- the substrate particles according to the present invention are used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer. That is, the base particle according to the present invention is a base particle for conductive particles.
- the compression recovery rate of the base particles according to the present invention is less than 50%.
- the base particles according to the present invention have a low compression recovery rate, and the base particles have an appropriate hardness in the initial stage of compression. Furthermore, in the base particle which concerns on this invention, hardness changes in the stage compressed to some extent, and a more flexible property is expressed. For this reason, deformation in the middle period (30% compression deformation time point) occurs at a load value that is not much different from the load value at the initial deformation time point (10% compression deformation time point).
- the binder resin is sufficiently eliminated by the hardness that is initially expressed, and the conductive layer Alternatively, the oxide film on the surface of the electrode can be sufficiently penetrated, and the contact area between the electrode and the conductive particles can be sufficiently increased due to the flexibility in the middle period. Further, due to the mid-term flexibility, damage to the electrode and the substrate due to the conductive particles can be suppressed, and generation of cracks in the electrode can be suppressed.
- the base particles according to the present invention have a low compression recovery rate, after the connection between the electrodes, the repulsive force that the compressed conductive particles try to return to the original shape is reduced, and a phenomenon called spring back occurs. It becomes difficult to occur. Therefore, the use of the base particles according to the present invention can suppress poor connection due to cracks in the electrode and poor connection due to springback.
- the compression recovery rate of the base material particles is less than 50%.
- the compression recovery rate is preferably 40% or less, more preferably 30% or less.
- the repulsive force that the compressed conductive particles try to return to the original shape increases when the electrodes are connected, and a phenomenon called springback is likely to occur, Connection becomes unstable.
- the compression recovery rate can be measured as follows.
- ⁇ Spread base particles on the sample stage About one spread
- the load speed is 0.33 mN / sec.
- the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
- Compression recovery rate (%) [(L1-L2) / L1] ⁇ 100
- L1 Compression displacement from the load value for origin to the reverse load value when applying a load
- L2 Unloading displacement from the reverse load value to the load value for origin when releasing the load
- the 10% K value is preferably 3500 N / mm 2 or more, more preferably 4000 N / mm 2 or more, more preferably 4500N / mm 2 or more, particularly preferably 5000N / mm 2 or more, preferably 5500N / mm 2 or less .
- the 10% K value is equal to or more than the lower limit, the binder resin is effectively eliminated and the conductive film or the oxide film on the surface of the electrode is effectively penetrated, so that the connection resistance between the electrodes is effectively low. Become.
- the 10% K value is less than or equal to the above upper limit, cracks are more unlikely to occur in the electrode.
- the 10% K value is 4500 N / mm 2 or more, the connection resistance is effectively reduced. More preferably, when it is 5000 N / mm 2 or more, voids in the electrodes are hardly generated.
- the ratio of the 30% load value to the 10% load value (30% load value / 10% load value) is 3.0 or less.
- the ratio (30% load value / 10% load value) is more preferably 2.8 or less.
- the ratio (30% load value / 10% load value) is less than or equal to the above upper limit, the contact area between the electrode and the conductive particles is sufficiently large, the connection resistance between the electrodes is effectively reduced, and the electrode The connection reliability between them becomes even higher.
- the ratio (30% load value / 10% load value) is preferably 1.5 or more.
- Compression modulus when the base particle and 30% compressive deformation is preferably 3000N / mm 2 or less, more preferably 2500N / mm 2 or less.
- 30% K value is less than or equal to the above upper limit, the contact area between the conductive particles and the electrode is further increased, and cracks are more unlikely to occur in the electrode.
- the 30% K value is preferably 500 N / mm 2 or more.
- the 10% K value is 3000 N / mm 2 or less, cracks are more unlikely to occur in the electrode.
- the 10% K value is 2300 N / mm 2 or less, cracks are hardly generated in the electrode.
- the ratio (40% load value / 10% load value) of the load value (40% load value) when the base material particle is compressed 40% to the load value (10% load value) when 10% compressed is preferable. 6 or less, more preferably 5 or less.
- the ratio (40% load value / 10% load value) is preferably 2 or more.
- the load value and the compressive elastic modulus (10% K value and 30% K value) in the base material particles can be measured as follows.
- the base material particles are compressed under the conditions of a cylindrical (100 ⁇ m diameter, diamond) smooth indenter end face at 25 ° C., 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 measured value obtained, the compression elastic modulus can be obtained by the following formula.
- the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
- the above-mentioned compression modulus expresses the hardness of the base particle universally and quantitatively.
- the compression elastic modulus By using the compression elastic modulus, the hardness of the base particle can be expressed quantitatively and uniquely.
- the fracture strain of the substrate particles is 10% or more and 30% or less.
- the load value at this changing point is the breaking load value
- the displacement amount is the breaking displacement.
- the ratio of the fracture displacement to the particle size before compression (fracture displacement / particle size before compression) ⁇ 100 is defined as fracture strain (%).
- fracture strain %.
- the fracture behavior of a particle having a particle size of 5 ⁇ m before compression is observed when the displacement is 1 ⁇ m
- the fracture strain is calculated as 20%.
- the fracture behavior of the shell is generally observed at the initial stage of displacement.
- the breaking strain is equal to or higher than the lower limit
- the exclusion property of the binder resin, the penetrability of the conductive layer and the oxide film of the electrode are further enhanced, and the connection resistance is further lowered.
- the fracture strain is less than or equal to the above upper limit, mid-term flexibility is exhibited, the contact area between the conductive particles and the electrode is further increased, and the connection resistance is further decreased.
- the above-mentioned fracture strain can be evaluated from the above-described measurement of the compressive elastic modulus, and can be measured by reading the displacement amount at the discontinuous point of the compression displacement curve.
- the particle size of the core is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, particularly preferably 20 ⁇ m or less, and most preferably 10 ⁇ m or less.
- the core particle size is not less than the above lower limit and not more than the above upper limit, 10% K value, 30% K value, the above ratio (30% load value / 10% load value) and the above ratio (40% load value / 10) % Load value) is easy to show a suitable value, and the base particles can be suitably used for the use of conductive particles.
- the core particle diameter is not less than the lower limit and not more than the upper limit
- the contact area between the conductive particles and the electrodes is sufficiently large, and Aggregated conductive particles are hardly formed when the conductive layer is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
- the particle diameter of the core means a diameter when the core is a true sphere, and when the core is a shape other than a true sphere, means a diameter when assuming a true sphere corresponding to the volume. To do.
- the particle size of a core means the average particle size which measured the core with the arbitrary particle size measuring apparatus. For example, a particle size distribution measuring machine using principles such as laser light scattering, electrical resistance value change, and image analysis after imaging can be used.
- the base particle is a core-shell particle including a core and a shell disposed on the surface of the core.
- the core shell particle compression recovery rate, 10% K value, 30% K value, the above ratio (30% load value / 10% load value) and the above ratio (40% load value / 10% load value) satisfy the above-mentioned values. By doing so, the connection resistance between electrodes can be made low and the connection reliability between electrodes can be improved.
- the core is preferably an organic core.
- the shell is preferably an inorganic shell. It is preferable that the core is an organic core and the shell is an inorganic shell.
- the substrate particles include an organic core and an inorganic shell disposed on the surface of the organic core, and are preferably core-shell particles, and are preferably core-shell type organic-inorganic hybrid particles.
- the compression recovery rate, 10% K value, 30% K value, the ratio (30% load value / 10% load value) and the ratio ( (40% load value / 10% load value) can easily satisfy the above-described value.
- the core is preferably an organic core, and is preferably organic particles. Since the organic core and the organic particles are relatively soft compared to the inorganic core and the inorganic particles, a shell is formed on the surface of the relatively soft organic core. As a result, the compression recovery rate, the ratio (30% It is easy to satisfy (load value / 10% load value) and the above ratio (40% load value / 10% load value).
- Various organic materials are preferably used as a material for forming the organic core.
- the material for forming the organic core include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Polymerize one or more of polyalkylene terephthalate, polysulfone, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, and various polymerizable monomers having ethylenically unsaturated groups The polymer obtained by making it use is used. Easily design and synthesize base particles with any compression properties suitable for conductive materials by polymerizing one or more of various polymerizable monomers having ethylenically unsaturated groups
- the organic core is obtained by polymerizing a monomer having an ethylenically unsaturated group
- the monomer having an ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer.
- a polymer a polymer having an ethylenically unsaturated group
- non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; acids such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate Atom
- crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane
- the organic core can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method.
- this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
- the compression modulus when the core is compressed 10% 10% K value
- the compression recovery rate of the core is preferably less than 50%, more preferably 40% or less, still more preferably 30% or less. If the core satisfies the 10% K value or the compression modulus, the 10% K value of the base particle having the core covered with an inorganic shell, the ratio (10% load value / 30% load value) and the compression recovery rate can be easily controlled within a suitable range.
- the method of designing the physical properties of the core within the above-mentioned range is not limited.
- a crosslinkable polymer is used as a compound for forming the core.
- examples thereof include a method using 70% by weight or less and 10% by weight or more of a non-crosslinkable monomer having an alicyclic skeleton.
- non-crosslinkable monomers having an alicyclic skeleton include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.
- a monomer having an ethylenically unsaturated group is absorbed into a granulated product obtained by polycondensing a silane coupling agent such as vinyltrimethoxysilane or (meth) acryloxytrimethoxysilane by a sol-gel technique.
- a silane coupling agent such as vinyltrimethoxysilane or (meth) acryloxytrimethoxysilane by a sol-gel technique.
- the material constituting the core may contain not only an organic compound but also a compound having a silicon atom.
- the ratio of the carbon atom content in the core to the silicon atom content (carbon atom content / silicon atom content) is preferably 1.2 or more.
- a core having the above ratio (carbon atom content / silicon atom content) of 1.2 or more corresponds to an organic core.
- the decomposition temperature of the core is preferably more than 200 ° C, more preferably more than 250 ° C, and still more preferably 300 ° C. Exceed.
- the decomposition temperature of the core may exceed 400 ° C., may exceed 500 ° C., may exceed 600 ° C., and may exceed 800 ° C.
- the base material particles are core-shell particles.
- the shell is disposed on the surface of the core.
- the shell preferably covers the surface of the core.
- the shell is preferably an inorganic shell.
- the inorganic shell preferably contains 50% by weight or more of silicon atoms.
- the inorganic shell is an inorganic shell containing silicon atoms as a main component.
- the said inorganic shell may contain the carbon atom, even when it contains a carbon atom, if a silicon atom is a main component, it will be called an inorganic shell.
- the inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material.
- a sol-gel method it is easy to dispose a shell-like material on the surface of the core.
- the base material particles after the firing, the core remains without being removed by volatilization or the like.
- the said base particle is equipped with the said core after baking. If the core is removed by volatilization or the like after firing, the 10% K value becomes considerably low.
- an interfacial sol reaction is performed by coexisting an inorganic monomer such as tetraethoxysilane in a dispersion containing a core, a solvent such as water or alcohol, a surfactant, and a catalyst such as an aqueous ammonia solution.
- the metal alkoxide is preferably hydrolyzed and polycondensed.
- the metal alkoxide is preferably made into a shell by a sol-gel method.
- the surfactant is not particularly limited.
- the surfactant is appropriately selected and used so as to form a good shell.
- examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Among these, a cationic surfactant is preferable because a good inorganic shell can be formed.
- cationic surfactant examples include quaternary ammonium salts and quaternary phosphonium salts. Specific examples of the cationic surfactant include hexadecyl ammonium bromide.
- the shell-like material is preferably baked.
- the degree of crosslinking in the inorganic shell can be adjusted by the firing conditions.
- the 10% K value and the 30% K value of the base material particles are more suitable as compared with the case where the firing is not performed.
- the 10% K value is sufficiently increased by increasing the degree of crosslinking.
- the inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material at 100 ° C. or higher (firing temperature).
- the firing temperature is more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher.
- the degree of crosslinking in the inorganic shell becomes more appropriate, and the 10% K value, 30% K value, the ratio (30% load value / 10% load value) and the ratio ( (40% load value / 10% load value) shows a more preferable value, and the base particles can be used more suitably depending on the use of the conductive particles.
- the inorganic shell is formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method, and then firing the shell-like material at a temperature lower than the decomposition temperature (firing temperature) of the organic core. It is preferable.
- the firing temperature is preferably 10 ° C. or more lower than the decomposition temperature of the core, and more preferably 50 ° C. or more lower than the decomposition temperature of the core.
- the firing temperature is preferably 500 ° C. or lower, more preferably 300 ° C. or lower, and still more preferably 200 ° C. or lower.
- the metal alkoxide examples include silane alkoxide, titanium alkoxide, zirconium alkoxide, and aluminum alkoxide.
- the metal alkoxide is preferably silane alkoxide, titanium alkoxide, zirconium alkoxide or aluminum alkoxide, more preferably silane alkoxide, titanium alkoxide or zirconium alkoxide, and silane alkoxide. More preferably.
- the metal atom in the metal alkoxide is preferably a silicon atom, a titanium atom, a zirconium atom or an aluminum atom, more preferably a silicon atom, a titanium atom or a zirconium atom. More preferably, it is a silicon atom.
- the said metal alkoxide only 1 type may be used and 2 or more types may be used together.
- the metal alkoxide is preferably a metal alkoxide represented by the following formula (1).
- M is a silicon atom, a titanium atom or a zirconium atom
- R1 is a phenyl group, an alkyl group having 1 to 30 carbon atoms, an organic group having 1 to 30 carbon atoms having a polymerizable double bond, or It represents an organic group having 1 to 30 carbon atoms having an epoxy group
- R2 represents an alkyl group having 1 to 6 carbon atoms
- n represents an integer of 0 to 2.
- n is 2
- the plurality of R1s may be the same or different.
- Several R2 may be the same and may differ.
- the metal alkoxide is preferably a silane alkoxide represented by the following formula (1A).
- R1 represents a phenyl group, an alkyl group having 1 to 30 carbon atoms, an organic group having 1 to 30 carbon atoms having a polymerizable double bond, or an organic group having 1 to 30 carbon atoms having an epoxy group.
- R2 represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2.
- n represents 2
- the plurality of R1s may be the same or different.
- Several R2 may be the same and may differ.
- n in the above formula (1A) preferably represents 0 or 1, and more preferably represents 0. When the content of silicon atoms contained in the shell is high, the effect of the present invention is more excellent.
- R1 is an alkyl group having 1 to 30 carbon atoms
- specific examples of R1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, And an n-decyl group.
- This alkyl group preferably has 10 or less carbon atoms, more preferably 6 or less.
- the alkyl group includes a cycloalkyl group.
- Examples of the polymerizable double bond include a carbon-carbon double bond.
- R1 is an organic group having 1 to 30 carbon atoms having a polymerizable double bond
- specific examples of R1 include a vinyl group, an allyl group, an isopropenyl group, and a 3- (meth) acryloxyalkyl group.
- Examples of the (meth) acryloxyalkyl group include a (meth) acryloxymethyl group, a (meth) acryloxyethyl group, and a (meth) acryloxypropyl group.
- the number of carbon atoms of the organic group having 1 to 30 carbon atoms having a polymerizable double bond is preferably 2 or more, preferably 30 or less, more preferably 10 or less.
- (meth) acryloxy means methacryloxy or acryloxy.
- R1 is an organic group having 1 to 30 carbon atoms having an epoxy group
- specific examples of R1 include 1,2-epoxyethyl group, 1,2-epoxypropyl group, 2,3-epoxypropyl group, Examples include 3,4-epoxybutyl group, 3-glycidoxypropyl group, and 2- (3,4-epoxycyclohexyl) ethyl group.
- the organic group having 1 to 30 carbon atoms having an epoxy group preferably has 8 or less carbon atoms, more preferably 6 or less.
- the organic group having 1 to 30 carbon atoms and having the epoxy group is a group containing an oxygen atom derived from an epoxy group in addition to a carbon atom and a hydrogen atom.
- R2 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
- R2 preferably represents a methyl group or an ethyl group.
- silane alkoxide examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxy.
- Examples include silane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and diisopropyldimethoxysilane. Silane alkoxides other than these may be used.
- the material of the shell In order to effectively increase the content of silicon atoms contained in the shell, it is preferable to use tetramethoxysilane or tetraethoxysilane as the material of the shell.
- the total content of tetramethoxysilane and tetraethoxysilane is preferably 50% by weight or more (or the total amount may be sufficient).
- the total content of the skeleton derived from tetramethoxysilane and the skeleton derived from tetraethoxysilane is preferably 50% by weight or more (or the total amount may be sufficient).
- titanium alkoxide examples include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, and the like. Titanium alkoxides other than these may be used.
- zirconium alkoxide examples include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide and the like. Other zirconium alkoxides may be used.
- the metal alkoxide preferably includes a metal alkoxide having a structure in which four oxygen atoms are directly bonded to a metal atom.
- the metal alkoxide preferably includes a metal alkoxide represented by the following formula (1a).
- M represents a silicon atom, a titanium atom or a zirconium atom
- R2 represents an alkyl group having 1 to 6 carbon atoms. Several R2 may be the same and may differ.
- the metal alkoxide preferably contains a silane alkoxide having a structure in which four oxygen atoms are directly bonded to a silicon atom. In this silane alkoxide, generally, four oxygen atoms are bonded to a silicon atom by a single bond.
- the metal alkoxide preferably includes a silane alkoxide represented by the following formula (1Aa).
- R2 represents an alkyl group having 1 to 6 carbon atoms. Several R2 may be the same and may differ.
- the content of each of the silane alkoxides represented by is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 55 mol% or more, and particularly preferably 60 mol%.
- the total amount of metal alkoxide used to form the inorganic shell is a metal alkoxide having a structure in which four oxygen atoms are directly bonded to the metal atom, the metal alkoxide represented by the formula (1a), the silicon atom May be a silane alkoxide having a structure in which four oxygen atoms are directly bonded to each other, or a silane alkoxide represented by the above formula (1Aa).
- the number ratio is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 55 mol% or more, and particularly preferably 60% or more.
- the ratio of the number of metal atoms to which four oxygen atoms are directly bonded is preferably 20% or more, more preferably 40% or more, among 100% of the total number of metal atoms contained in the inorganic shell. Preferably it is 50% or more, still more preferably 55 mol% or more, and particularly preferably 60% or more.
- the metal alkoxide is a silane alkoxide and contained in the inorganic shell.
- the ratio is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 55% or more, and particularly preferably 60% or more.
- a silicon atom in which four —O—Si groups are directly bonded and four oxygen atoms in the four —O—Si groups are directly bonded is represented by, for example, the following formula (11). It is a silicon atom in the structure. Specifically, it is a silicon atom indicated by an arrow A in the structure represented by the following formula (11X).
- the oxygen atom in the above formula (11) generally forms a siloxane bond with the adjacent silicon atom.
- the ratio of the number of silicon atoms in which four —O—Si groups are directly bonded and the four oxygen atoms in the four —O—Si groups are directly bonded (the ratio of the number of Q4 (%)).
- Q4 four —O—Si groups are directly bonded and four oxygen atoms in the four —O—Si groups are directly bonded to each other.
- the peak area of silicon atoms) and Q1 to Q3 (1 to 3 —O—Si groups are directly bonded, and 1 to 3 oxygen atoms in 1 to 3 of the above —O—Si groups are directly bonded. And the peak area of silicon atoms).
- the thickness of the shell is preferably 100 nm or more, more preferably 200 nm or more, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
- the thickness of the shell is an average thickness per base particle. The thickness of the shell can be controlled by controlling the sol-gel method.
- the thickness of the shell can be determined from the difference in average value between the particle diameter of the base particle and the core particle diameter.
- the particle diameter of the base particle means a diameter when the base particle is a true sphere, and when the base particle is a shape other than a true sphere, it is assumed to be a true sphere corresponding to its volume. This means the diameter when
- a particle size distribution measuring machine using principles such as laser light scattering, electric resistance value change, image analysis after imaging can be used.
- the aspect ratio of the substrate particles is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.2 or less.
- the aspect ratio indicates a major axis / minor axis.
- the said electroconductive particle is equipped with the base material particle mentioned above and the conductive layer arrange
- FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
- the conductive particle 1 has a base particle 11 and a conductive layer 2 disposed on the surface of the base particle 11.
- the conductive layer 2 covers the surface of the base particle 11.
- the conductive particle 1 is a coated particle in which the surface of the base particle 11 is coated with the conductive layer 2.
- the base particle 11 includes a core 12 and a shell 13 disposed on the surface of the core 12.
- the shell 13 covers the surface of the core 12.
- the conductive layer 2 is disposed on the surface of the shell 13.
- the conductive layer 2 covers the surface of the shell 13.
- FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
- the conductive layer 22 has the base particle 11 and the conductive layer 22 arranged on the surface of the base particle 11.
- the conductive layer 22 includes a first conductive layer 22A that is an inner layer and a second conductive layer 22B that is an outer layer.
- the first conductive layer 22 ⁇ / b> A is disposed on the surface of the base particle 11.
- a second conductive layer 22B is disposed on the surface of the first conductive layer 22A.
- FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
- the 3 includes the base particle 11, the conductive layer 32, a plurality of core substances 33, and a plurality of insulating substances 34.
- the conductive layer 32 is disposed on the surface of the base particle 11.
- a conductive layer 32 is disposed on the surface of the shell 13.
- the conductive particles 31 have a plurality of protrusions 31a on the conductive surface.
- the conductive layer 32 has a plurality of protrusions 32a on the outer surface.
- the conductive particles may have protrusions on the conductive surface or may have protrusions on the outer surface of the conductive layer.
- a plurality of core substances 33 are arranged on the surface of the base particle 11.
- a plurality of core materials 33 are arranged on the surface of the shell 13.
- the plurality of core materials 33 are embedded in the conductive layer 32.
- the core substance 33 is disposed inside the protrusions 31a and 32a.
- the conductive layer 32 covers a plurality of core materials 33.
- the outer surface of the conductive layer 32 is raised by the plurality of core materials 33, and protrusions 31a and 32a are formed.
- the conductive particles 31 have an insulating substance 34 disposed on the outer surface of the conductive layer 32. At least a part of the outer surface of the conductive layer 32 is covered with an insulating material 34.
- the insulating substance 34 is made of an insulating material and is an insulating particle.
- the said electroconductive particle may have the insulating substance arrange
- the metal for forming the conductive layer 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 these. And the like.
- the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes can be made still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.
- the conductive layer may be formed of a single layer.
- the conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked 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 these preferred conductive layers, the connection resistance between the electrodes is further reduced.
- the outermost layer is a gold layer, the corrosion resistance is further enhanced.
- the method for forming the conductive layer on the surface of the substrate particles is not particularly limited.
- a method for forming the conductive layer for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc.
- the method by electroless plating is preferable.
- the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
- the particle size of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 520 ⁇ m or less, more preferably 500 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, and particularly preferably 20 ⁇ m. It is as follows. When the particle size of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrode becomes sufficiently large when the conductive particles are used to connect the electrodes, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles.
- the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
- the particle size 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 the conductive material.
- the particle diameter of the conductive particles means a diameter when the conductive particles are spherical, and when the conductive particles have a shape other than the true spherical shape, it is assumed that the volume is a true sphere. Means the diameter.
- the thickness of the conductive layer 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 even more preferably 0.3 ⁇ m or less.
- the thickness of the conductive layer is the thickness of the entire conductive layer when the conductive layer is a multilayer. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting the electrodes. .
- the thickness of the outermost conductive layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably 0. .1 ⁇ m or less.
- the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes is further increased. Lower. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.
- the thickness of the conductive layer 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 conductive particles may have protrusions on the conductive surface.
- the conductive particles may have protrusions on the outer surface of the conductive layer. It is preferable that there are a plurality of the protrusions.
- An oxide film is often formed on the surface of the conductive layer and the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively eliminated by the protrusions by placing the conductive particles between the electrodes and pressing them. For this reason, an electrode and the conductive layer of electroconductive particle can be contacted still more reliably, and the connection resistance between electrodes can be made low.
- the conductive particles are provided with 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 or binder resins in between can be effectively eliminated. For this reason, the conduction
- a method of forming protrusions on the surface of the conductive particles a method of forming a conductive layer by electroless plating after attaching a core substance to the surface of the base particles, and electroless plating on the surface of the base particles Examples include a method of forming a conductive layer by, attaching a core substance, and further forming a conductive layer by electroless plating.
- the core material may not be used to form the protrusion.
- the conductive particles may include an insulating material disposed on the outer surface of the conductive layer.
- an insulating material disposed on the outer surface of the conductive layer.
- 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 substance between the conductive layer of an electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes in the case of the connection between electrodes.
- the insulating substance is preferably an insulating resin layer or insulating particles, and more preferably insulating particles.
- the insulating particles are preferably insulating resin particles.
- the conductive material includes the conductive particles described above and a binder resin.
- the conductive particles are preferably dispersed in a binder resin and used as a conductive material.
- the conductive material is preferably an anisotropic conductive material.
- the conductive material is preferably used for electrical connection of electrodes.
- the conductive material is preferably a circuit connection material.
- the binder resin is not particularly limited.
- a known insulating resin is used.
- the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers.
- the said binder resin 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.
- a filler 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 an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
- the binder resin after curing is high in flexibility, the springback is further suppressed, so that the effects of the present invention can be further exhibited.
- the method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used.
- Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse
- distributing is mentioned.
- the conductive material can be used as a conductive paste and a conductive film.
- the conductive material according to the present invention 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 resin 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 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less.
- the content of the binder resin 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 is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 40% by weight or less, more preferably 20% by weight or less, More preferably, it is 10 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.
- connection structure can be obtained by connecting the connection target members using the conductive particles described above or using a conductive material including the conductive particles described above and a binder resin.
- connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection portion.
- connection portion connecting the first connection target member and the second connection target member, and the connection portion.
- the connection part is the 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.
- the first connection object member preferably has a first electrode on the surface.
- the second connection target member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode are electrically connected by the conductive particles.
- FIG. 4 is a front cross-sectional view schematically showing a connection structure using the conductive particles 1 shown in FIG.
- connection structure 51 shown in FIG. 4 is a connection that connects 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 connection part 54 is formed of a conductive material containing the conductive particles 1 and a binder resin.
- 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 52 has a plurality of first electrodes 52a on the surface (upper surface).
- the second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface).
- the first electrode 52 a and the second electrode 53 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
- 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 pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
- the heating temperature is about 120 to 220 ° C.
- the pressure applied to connect the electrode of the flexible printed board, the electrode disposed on the resin film, and the electrode of the touch panel is about 9.8 ⁇ 10 4 to 1.0 ⁇ 10 6 Pa.
- connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards.
- 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 printed circuit board or a connection target member in which an electrode is disposed on the surface of a resin film.
- the connection target member is preferably a flexible printed board, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film.
- the flexible printed board generally has electrodes on the surface.
- the initial hardness of the base particles is designed in an appropriate range in order to suppress damage to the connection target member such as the substrate of the conductive particles. For this reason, in this invention, when a comparatively thin glass substrate (about 0.2 mm) and a flexible printed circuit board are connected, a big effect is exhibited.
- the combination of the first and second connection target members is preferably a combination of a glass substrate and a flexible printed circuit board.
- the first connection target member may be a glass substrate
- the second connection target member may be a glass substrate.
- the thickness of the glass substrate is preferably 0.05 mm or more and less than 0.5 mm.
- 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 copper electrode, a molybdenum electrode, a tungsten electrode, and a titanium electrode.
- metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a tungsten electrode, and a titanium electrode.
- a great effect is exhibited particularly in the case of a titanium electrode.
- At least one of the first and second electrodes is preferably a titanium electrode, and both of the first and second electrodes are preferably titanium electrodes.
- at least one of the materials constituting the surfaces of the first and second electrodes contains titanium, and both the materials constituting the surfaces of the first and second electrodes contain titanium. Is more preferable.
- Example 1 Production of base particles Production of core) 600 parts by weight of divinylbenzene (purity 96% by weight) and 400 parts by weight of isobornyl acrylate were mixed to obtain a mixed solution. 20 parts by weight of benzoyl peroxide was added to the obtained mixed solution and stirred until it was uniformly dissolved to obtain a monomer mixed solution. 4000 parts by weight of a 2% by weight aqueous solution in which polyvinyl alcohol having a molecular weight of about 1700 was dissolved in pure water was placed in a reaction kettle. Into this, the obtained monomer mixture was put and stirred for 4 hours to adjust the particle size so that the monomer droplets had a predetermined particle size.
- reaction was performed in a nitrogen atmosphere at 85 ° C. for 9 hours, and the polymerization reaction of monomer droplets was performed to obtain particles.
- the obtained particles were washed several times with hot water, and then classified to recover polymer particles (organic cores) having several different particle sizes.
- Example 1 among the polymer particles recovered by the classification operation, polymer particles (organic core) having a particle size of 3.00 ⁇ m were prepared.
- Preparation of core-shell particles 30 parts by weight of the obtained polymer particles (organic core), 12 parts by weight of hexadecylammonium bromide as a surfactant, 24 parts by weight of a 25% by weight aqueous ammonia solution, 540 parts by weight of methanol and 60 parts by weight of pure water It put in the part and mixed and obtained the dispersion liquid of a polymer particle. 120 parts by weight of tetraethoxysilane was added to this dispersion, and a condensation reaction by a sol-gel reaction was performed. A condensate of tetraethoxysilane was deposited on the surface of the polymer particles to form a shell, thereby obtaining particles.
- the obtained particles were washed several times with ethanol and dried to obtain core-shell particles (base material particles).
- the obtained core-shell particles had a particle size of 4.02 ⁇ m. From the core particle diameter and the core-shell particle diameter, the thickness of the shell was calculated to be 0.51 ⁇ m.
- the obtained base particles were washed and dried. Then, the nickel layer was formed in the surface of the obtained base material particle
- the nickel layer had a thickness of 0.1 ⁇ m.
- Example 2 Among the polymer particles recovered by the classification operation in Example 1, polymer particles (organic core) having a particle size of 2.50 ⁇ m were prepared. Use of the obtained polymer particles, and when producing core-shell particles, 540 parts by weight of methanol was changed to 540 parts by weight of isopropyl alcohol, and the addition amount of tetraethoxysilane was changed to 140 parts by weight. Except that, core-shell particles and conductive particles were obtained in the same manner as in Example 1.
- Example 3 Among the polymer particles recovered by the classification operation in Example 1, polymer particles (organic core) having a particle size of 2.25 ⁇ m were prepared. Use of the obtained polymer particles, and when producing core-shell particles, 540 parts by weight of methanol was changed to 540 parts by weight of isopropyl alcohol, and the addition amount of tetraethoxysilane was changed to 310 parts by weight. Except that, core-shell particles and conductive particles were obtained in the same manner as in Example 1.
- Example 4 The base material particles obtained in Example 1 were heat-treated at 200 ° C. for 30 minutes in a state where nitrogen was filled in an electric furnace. Thereafter, conductive particles were produced in the same manner as in Example 1.
- Example 5 Palladium adhesion process
- the base material particle obtained in Example 1 was prepared. The obtained substrate particles were etched and washed with water. Next, the base particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- Electroless nickel plating step In the same manner as in Example 1, a nickel layer was formed on the surface of the substrate particles to produce conductive particles.
- the nickel layer had a thickness of 0.1 ⁇ m.
- Example 6 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
- the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
- Example 2 10 g of the conductive particles obtained in Example 1 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
- Example 7 Among the polymer particles recovered by the classification operation in Example 1, polymer particles (organic core) having a particle size of 2.50 ⁇ m were prepared. Other than using the obtained polymer particles and changing the amount of tetraethoxysilane to 140 parts by weight when the core-shell particles were prepared, 540 parts by weight of methanol was changed to 540 parts by weight of acetonitrile. Produced core-shell particles and conductive particles in the same manner as in Example 1.
- Example 8 Among the polymer particles recovered by the classification operation in Example 1, polymer particles (organic core) having a particle size of 2.75 ⁇ m were prepared. Using the obtained polymer particles, and changing the 540 parts by weight of methanol to 540 parts by weight of isopropyl alcohol and changing the addition amount of tetraethoxysilane to 50 parts by weight when preparing the core-shell particles. Except that, core-shell particles and conductive particles were obtained in the same manner as in Example 1.
- Example 9 Among the polymer particles recovered by the classification operation in Example 1, polymer particles (organic core) having a particle size of 2.75 ⁇ m were prepared. Other than using the obtained polymer particles and changing the amount of methanol added to 540 parts by weight of acetonitrile and changing the amount of tetraethoxysilane added to 50 parts by weight when preparing the core-shell particles. Produced core-shell particles and conductive particles in the same manner as in Example 1.
- Example 10 The substrate particles obtained in Example 1 were overheated at 200 ° C. for 30 minutes in a state filled with nitrogen in an electric furnace. Thereafter, conductive particles were obtained by the same treatment as in Example 1.
- Example 11 Among the polymer particles classified and recovered in Example 1, polymer particles (organic core) having a particle diameter of 3.5 ⁇ m were prepared. Except that the obtained polymer particles were used and that the core-shell particles were produced, that 540 parts by weight of methanol was changed to 540 parts by weight of acetonitrile, and the addition amount of tetraethoxysilane was changed to 50 parts by weight. In the same manner as in Example 1, core-shell particles and conductive particles were obtained.
- Example 1 (Comparative Example 1) Among the polymer particles recovered in the classification operation in Example 1, polymer particles having a particle size of 3.00 ⁇ m were prepared. Using the obtained polymer particles as base particles, conductive particles were obtained in the same manner as in Example 1.
- Comparative Example 2 In preparing the core, 600 parts by weight of divinylbenzene (purity 96% by weight) and 400 parts by weight of isobornyl acrylate were changed to 950 parts by weight of 1,4-butanediol diacrylate and 50 parts by weight of ethylene glycol dimethacrylate. Except that, particles were obtained in the same manner as in Example 1. After the obtained particles were washed several times with hot water, classification operation was performed to collect several kinds of polymer particles having different particle sizes.
- Comparative Example 2 polymer particles having a particle size of 3.02 ⁇ m were prepared from the polymer particles recovered by the classification operation. Using the obtained polymer particles as base particles, conductive particles were obtained in the same manner as in Example 1.
- Comparative Example 3 polymer particles having a particle size of 3.01 ⁇ m were prepared from the polymer particles recovered by the classification operation. Using the obtained polymer particles as base particles, conductive particles were obtained in the same manner as in Example 1.
- Example 4 Among the polymer particles recovered in the classification operation in Example 1, polymer particles having a particle size of 3.00 ⁇ m were prepared. When producing core-shell particles using the obtained polymer particles, core-shell particles and conductive particles are obtained in the same manner as in Example 1 except that the amount of tetraethoxysilane added is changed to 10 parts by weight. It was.
- Compressive elastic modulus (10% K value and 30% K value) of substrate particles, and 10% load value, 30% load value, and 40% load value
- Fracture strain of substrate particles Using a micro compression tester (“Fischerscope H-100” manufactured by Fischer), fracture strain was measured by the method described above at 23 ° C.
- connection resistance Fabrication of connection structure 10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei E-material) 50 parts by weight of “HX3941HP” manufactured by KK And dispersed to obtain a resin composition.
- Bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation)
- acrylic rubber weight average molecular weight of about 800,000
- methyl ethyl ketone 200 parts by weight of methyl ethyl ketone
- microcapsule type curing agent Asahi Kasei E-material 50 parts by weight of “HX3941HP” manufactured by KK And dispersed to obtain a resin composition.
- the obtained resin composition was applied to a 50 ⁇ m-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film.
- the thickness of the obtained anisotropic conductive film was 12 ⁇ m.
- the obtained anisotropic conductive film was cut into a size of 5 mm ⁇ 5 mm.
- the two-layer flexible printed circuit board width 2cm, length 1cm
- a laminate of the PET substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure.
- the two-layer flexible printed board by which the copper electrode was formed in the polyimide film and the copper electrode surface was Au-plated was used.
- Connection resistance measurement The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. Connection resistance was determined according to the following criteria.
- connection resistance is 3.0 ⁇ or less ⁇ : Connection resistance exceeds 3.0 ⁇ , 4.0 ⁇ or less ⁇ : Connection resistance exceeds 4.0 ⁇ , 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇
- ⁇ There is no number of cracks generated in 100 electrodes. ⁇ : The number of cracks generated in 100 electrodes is 2 or less. ⁇ : Cracks are generated in 100 electrodes. The number is 3 to 5 ⁇ : out of 100 electrodes, the number of cracks is 6 to 10 XX: out of 100 electrodes, the number of cracks is 11 or more
- Example 1 The results are shown in Table 1 below.
- the aspect ratios of the base particles obtained in Examples 1 to 4 and 7 to 11 were all 1.2 or less.
- the connection resistance evaluation results in Examples 3 to 5 and 10 are all “ ⁇ ”, but the connection resistance value in Example 5 is lower than the connection resistance value in Examples 3, 4 and 10. It was. Protrusions are thought to be influencing.
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Abstract
Description
本発明に係る基材粒子は、表面上に導電層が形成され、該導電層を有する導電性粒子を得るために用いられる。すなわち、本発明に係る基材粒子は、導電性粒子用基材粒子である。
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
F:基材粒子が10%又は30%圧縮変形したときの荷重値(N)
S:基材粒子が10%又は30%圧縮変形したときの圧縮変位(mm)
R:基材粒子の半径(mm)
上記式(1)中、Mはケイ素原子、チタン原子又はジルコニウム原子であり、R1はフェニル基、炭素数1~30のアルキル基、重合性二重結合を有する炭素数1~30の有機基又はエポキシ基を有する炭素数1~30の有機基を表し、R2は炭素数1~6のアルキル基を表し、nは0~2の整数を表す。nが2であるとき、複数のR1は同一であってもよく、異なっていてもよい。複数のR2は同一であってもよく、異なっていてもよい。
上記式(1A)中、R1はフェニル基、炭素数1~30のアルキル基、重合性二重結合を有する炭素数1~30の有機基又はエポキシ基を有する炭素数1~30の有機基を表し、R2は炭素数1~6のアルキル基を表し、nは0~2の整数を表す。nが2であるとき、複数のR1は同一であってもよく、異なっていてもよい。複数のR2は同一であってもよく、異なっていてもよい。シェルに含まれるケイ素原子の含有量を効果的に高めるために、上記式(1A)中のnは0又は1を表すことが好ましく、0を表すことがより好ましい。シェルに含まれるケイ素原子の含有量が高いと、本発明の効果により一層優れる。
上記式(1a)中、Mはケイ素原子、チタン原子又はジルコニウム原子であり、R2は炭素数1~6のアルキル基を表す。複数のR2は同一であってもよく、異なっていてもよい。
上記式(1Aa)中、R2は炭素数1~6のアルキル基を表す。複数のR2は同一であってもよく、異なっていてもよい。
上記導電性粒子は、上述した基材粒子と、該基材粒子の表面上に配置された導電層とを備える。
上記導電材料は、上述した導電性粒子と、バインダー樹脂とを含む。上記導電性粒子は、バインダー樹脂中に分散され、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、電極の電気的な接続に好適に用いられる。上記導電材料は、回路接続材料であることが好ましい。
上述した導電性粒子を用いて、又は上述した導電性粒子とバインダー樹脂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。
(1)基材粒子の作製
コアの作製)
ジビニルベンゼン(純度96重量%)600重量部と、イソボロニルアクリレート400重量部とを混合し、混合液を得た。得られた混合液に過酸化ベンゾイル20重量部を加えて、均一に溶解するまで攪拌し、モノマー混合液を得た。分子量約1700のポリビニルアルコールを純水に溶解させた2重量%水溶液4000重量部を、反応釜に入れた。この中に、得られたモノマー混合液を入れ、4時間攪拌することで、モノマーの液滴が所定の粒径になるように、粒径を調整した。この後、85℃の窒素雰囲気下で9時間反応を行い、モノマー液滴の重合反応を行って、粒子を得た。得られた粒子を熱水にて数回洗浄した後、分級操作を行って、数種類の粒径の異なる重合体粒子(有機コア)を回収した。
得られた重合体粒子(有機コア)30重量部と、界面活性剤であるヘキサデシルアンモニウムブロミド12重量部と、25重量%のアンモニア水溶液24重量部とを、メタノール540重量部及び純水60重量部中に入れ、混合し、重合体粒子の分散液を得た。この分散液にテトラエトキシシラン120重量部を添加して、ゾルゲル反応による縮合反応を行った。テトラエトキシシランの縮合物を重合体粒子の表面に析出させて、シェルを形成し、粒子を得た。得られた粒子をエタノールで数回洗浄し、乾燥することでコアシェル粒子(基材粒子)を得た。得られたコアシェル粒子の粒径は4.02μmであった。コアの粒径とコアシェル粒子の粒径とから、シェルの厚みは0.51μmと算出された。
得られた基材粒子を洗浄し、乾燥した。その後、無電解めっき法により、得られた基材粒子の表面に、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。
実施例1にて分級操作で回収した重合体粒子のうち、粒径が2.50μmである重合体粒子(有機コア)を用意した。得られた重合体粒子を用いたこと、並びにコアシェル粒子を作製する際に、メタノール540重量部をイソプロピルアルコール540重量部に変更したこと、並びにテトラエトキシシランの添加量を140重量部に変更したこと以外は実施例1と同様にして、コアシェル粒子及び導電性粒子を得た。
実施例1にて分級操作で回収した重合体粒子のうち、粒径が2.25μmである重合体粒子(有機コア)を用意した。得られた重合体粒子を用いたこと、並びにコアシェル粒子を作製する際に、メタノール540重量部をイソプロピルアルコール540重量部に変更したこと、並びにテトラエトキシシランの添加量を310重量部に変更したこと以外は実施例1と同様にして、コアシェル粒子及び導電性粒子を得た。
実施例1にて得られた基材粒子を、電気炉にて窒素を充填した状態で、200℃で30分加熱処理を行った。その後実施例1と同様の処理にて、導電性粒子を作製した。
(1)パラジウム付着工程
実施例1で得られた基材粒子を用意した。得られた基材粒子をエッチングし、水洗した。次に、パラジウム触媒を8重量%含むパラジウム触媒化液100mL中に基材粒子を添加し、攪拌した。その後、ろ過し、洗浄した。pH6の0.5重量%ジメチルアミンボラン液に基材粒子を添加し、パラジウムが付着された基材粒子を得た。
パラジウムが付着された基材粒子をイオン交換水300mL中で3分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー(平均粒径100nm)1gを3分間かけて上記分散液に添加し、芯物質が付着された基材粒子を得た。
実施例1と同様にして、基材粒子の表面上に、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。
(1)絶縁性粒子の作製
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた1000mLのセパラブルフラスコに、メタクリル酸メチル100mmolと、N,N,N-トリメチル-N-2-メタクリロイルオキシエチルアンモニウムクロライド1mmolと、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩1mmolとを含むモノマー組成物を固形分率が5重量%となるようにイオン交換水に秤取した後、200rpmで攪拌し、窒素雰囲気下70℃で24時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒径220nm及びCV値10%の絶縁性粒子を得た。
実施例1にて分級操作で回収した重合体粒子のうち、粒径が2.50μmである重合体粒子(有機コア)を用意した。得られた重合体粒子を用いたこと、並びにコアシェル粒子を作製する際に、メタノール540重量部をアセトニトリル540重量部に変更したこと、並びにテトラエトキシシランの添加量を140重量部に変更したこと以外は実施例1と同様にして、コアシェル粒子及び導電性粒子を得た。
実施例1にて分級操作で回収した重合体粒子のうち、粒径が2.75μmである重合体粒子(有機コア)を用意した。得られた重合体粒子を用いたこと、並びにコアシェル粒子を作製する際に、メタノール540重量部をイソプロピルアルコール540重量部に変更したこと、並びにテトラエトキシシランの添加量を50重量部に変更したこと以外は実施例1と同様にして、コアシェル粒子及び導電性粒子を得た。
実施例1にて分級操作で回収した重合体粒子のうち、粒径が2.75μmである重合体粒子(有機コア)を用意した。得られた重合体粒子を用いたこと、並びにコアシェル粒子を作製する際に、メタノール540重量部をアセトニトリル540重量部に変更したこと、並びにテトラエトキシシランの添加量を50重量部に変更したこと以外は実施例1と同様にして、コアシェル粒子及び導電性粒子を得た。
実施例1で得られた基材粒子を、電気炉にて窒素を充填した状態で、200℃で30分過熱処理を行った。その後実施例1と同様の処理にて、導電性粒子を得た。
実施例1にて分級回収した重合体粒子のうち、粒子径が3.5μmである重合体粒子(有機コア)を用意した。得られた重合体粒子を用いたこと、並びにコアシェル粒子を作製する際に、メタノール540重量部をアセトニトリル540重量部に変更したこと、テトラエトキシシランの添加量を50重量部に変更したこと以外は実施例1と同様にして、コアシェル粒子及び導電性粒子を得た。
実施例1にて分級操作で回収した重合体粒子のうち、粒径が3.00μmである重合体粒子を用意した。得られた重合体粒子を基材粒子として用いて、実施例1と同様にして導電性粒子を得た。
コアを作製する際に、ジビニルベンゼン(純度96重量%)600重量部及びイソボロニルアクリレート400重量部を、1,4-ブタンジオールジアクリレート950重量部及びエチレングリコールジメタクリレート50重量部に変更したこと以外は実施例1と同様にして、粒子を得た。得られた粒子を熱水にて数回洗浄した後、分級操作を行って、数種類の粒径の異なる重合体粒子を回収した。
コアを作製する際に、ジビニルベンゼン(純度96重量%)600重量部及びイソボロニルアクリレート400重量部を、ジビニルベンゼン(純度96重量%)1000重量部に変更したこと、並びに過酸化ベンゾイルの添加量を40重量部に変更したこと以外は実施例1と同様にして、粒子を得た。得られた粒子を熱水にて数回洗浄した後、分級操作を行って、数種類の粒径の異なる重合体粒子を回収した。
実施例1にて分級操作で回収した重合体粒子のうち、粒径が3.00μmである重合体粒子を用意した。得られた重合体粒子を用いて、コアシェル粒子を作製する際に、テトラエトキシシランの添加量を10重量部に変更したこと以外は実施例1と同様にして、コアシェル粒子及び導電性粒子を得た。
(1)基材粒子の粒径、コアの粒径及びシェルの厚み
得られた基材粒子について、粒度分布測定装置(ベックマンコールター社製「Multisizer3」)を用いて、約10000個の粒径を測定し、平均粒径及び標準偏差等を測定した。基材粒子を作製する際に用いたコアについても、同様の方法により粒径を測定した。基材粒子の粒径とコアの粒径との差から、シェルの厚みを求めた。
得られた基材粒子の上記圧縮弾性率(10%K値及び30%K値)、並びに10%荷重値及び30%荷重値及び40%荷重値を、23℃の条件で、上述した方法により、微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて測定した。
得られた基材粒子の上記圧縮回復率を、上述した方法により、微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて測定した。
微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて、23℃の条件で、上述した方法により、破壊歪を測定した。
接続構造体の作製:
ビスフェノールA型エポキシ樹脂(三菱化学社製「エピコート1009」)10重量部と、アクリルゴム(重量平均分子量約80万)40重量部と、メチルエチルケトン200重量部と、マイクロカプセル型硬化剤(旭化成イーマテリアルズ社製「HX3941HP」)50重量部と、シランカップリング剤(東レダウコーニングシリコーン社製「SH6040」)2重量部とを混合し、導電性粒子を含有量が3重量%となるように添加し、分散させ、樹脂組成物を得た。
得られた接続構造体の対向する電極間の接続抵抗を4端子法により測定した。接続抵抗を下記の基準で判定した。
○○:接続抵抗が3.0Ω以下
○:接続抵抗が3.0Ωを超え、4.0Ω以下
△:接続抵抗が4.0Ωを超え、5.0Ω以下
×:接続抵抗が5.0Ωを超える
上記(5)接続抵抗の評価で得られた接続構造体の電極100個において、クラックが生じているか否かを観察した。
○○:電極100個のうち、クラックが生じている個数がない
○:電極100個のうち、クラックが生じている個数が2個以下である
△:電極100個のうち、クラックが生じている個数が3~5個である
×:電極100個のうち、クラックが生じている個数が6~10個である
××:電極100個のうち、クラックが生じている個数が11個以上である
上記(5)接続抵抗の評価で得られた接続構造体の電極100個において、金属顕微鏡を用いて、導電性微粒子が接触した電極部分における空隙の発生の有無を観察した。
○○:電極100個のうち、空隙が生じている電極がない
○:電極100個のうち、空隙が生じている個数が2個以下である
△:電極100個のうち、空隙が生じている個数が3~5個である
×:電極100個のうち、空隙が生じている個数が6個以上である
2…導電層
11…基材粒子
12…コア
13…シェル
21…導電性粒子
22…導電層
22A…第1の導電層
22B…第2の導電層
31…導電性粒子
31a…突起
32…導電層
32a…突起
33…芯物質
34…絶縁性物質
51…接続構造体
52…第1の接続対象部材
52a…第1の電極
53…第2の接続対象部材
53a…第2の電極
54…接続部
Claims (11)
- 表面上に導電層が形成され、前記導電層を有する導電性粒子を得るために用いられる基材粒子であって、
圧縮回復率が50%未満であり、
コアと、前記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あり、
10%圧縮したときの圧縮弾性率が3000N/mm2以上、かつ6000N/mm2未満であり、
30%圧縮したときの荷重値の10%圧縮したときの荷重値に対する比が3以下である、基材粒子。 - 前記コアが有機コアであり、
前記シェルが無機シェルである、請求項1に記載の基材粒子。 - 前記シェルの厚みが100nm以上、5μm以下である、請求項1又は2に記載の基材粒子。
- 30%圧縮したときの圧縮弾性率が3000N/mm2以下である、請求項1~3のいずれか1項に記載の基材粒子。
- 40%圧縮したときの荷重値の10%圧縮したときの荷重値に対する比が6以下である、請求項1~4のいずれか1項に記載の基材粒子。
- 破壊歪が10%以上、かつ30%以下である、請求項1~5のいずれか1項に記載の基材粒子。
- 請求項1~6のいずれか1項に記載の基材粒子と、
前記基材粒子の表面上に配置された導電層を備える、導電性粒子。 - 前記導電層の外表面上に配置された絶縁性物質をさらに備える、請求項7に記載の導電性粒子。
- 前記導電層の外表面に突起を有する、請求項7又は8に記載の導電性粒子。
- 導電性粒子と、バインダー樹脂とを含み、
前記導電性粒子が、請求項1~6のいずれか1項に記載の基材粒子と、前記基材粒子の表面上に配置された導電層とを備える、導電材料。 - 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、
前記接続部が、導電性粒子により形成されているか、又は前記導電性粒子とバインダー樹脂とを含む導電材料により形成されており、
前記導電性粒子が、請求項1~6のいずれか1項に記載の基材粒子と、前記基材粒子の表面上に配置された導電層とを備え、
前記第1の電極と前記第2の電極とが前記導電性粒子により電気的に接続されている、接続構造体。
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JP2014205759A (ja) * | 2013-04-12 | 2014-10-30 | 積水化学工業株式会社 | 有機無機ハイブリッド粒子、導電性粒子、導電材料及び接続構造体 |
JP5620608B1 (ja) * | 2012-12-28 | 2014-11-05 | 積水化学工業株式会社 | 有機無機ハイブリッド粒子、導電性粒子、導電材料及び接続構造体 |
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JPWO2014115468A1 (ja) | 2017-01-26 |
CN104704579B (zh) | 2018-09-28 |
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JP5559947B1 (ja) | 2014-07-23 |
CN104704579A (zh) | 2015-06-10 |
TWI598891B (zh) | 2017-09-11 |
TW201440078A (zh) | 2014-10-16 |
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