CN115699218A - Conductive particle, conductive material, and connection structure - Google Patents

Conductive particle, conductive material, and connection structure Download PDF

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Publication number
CN115699218A
CN115699218A CN202180039684.4A CN202180039684A CN115699218A CN 115699218 A CN115699218 A CN 115699218A CN 202180039684 A CN202180039684 A CN 202180039684A CN 115699218 A CN115699218 A CN 115699218A
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China
Prior art keywords
conductive
particles
conductive particles
resin
less
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CN202180039684.4A
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Chinese (zh)
Inventor
大日方秀平
松浦宽人
胁屋武司
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)

Abstract

Provided are conductive particles which can improve saturation magnetization, can reduce remanent magnetization, and can improve conduction reliability when electrodes are electrically connected. The conductive particle of the present invention includes a resin particle and a conductive portion disposed outside an outer surface of the resin particle, and the conductive particle includes the following configuration a, configuration B, or configuration C, and the configuration a: a magnetic body section including a magnetic body disposed between the resin particles and the conductive section, wherein a ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less; the composition B is as follows: the conductive portion contains a magnetic substance, and the ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less; and C: the resin particles include a magnetic body.

Description

Conductive particle, conductive material, and connection structure
Technical Field
The present invention relates to conductive particles that can be used for electrical connection between electrodes and the like. The present invention also relates to a conductive material and a connection structure using the conductive particles.
Background
Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin. In addition, as the conductive particles, conductive particles having base material particles and a conductive portion disposed on the surface of the base material particles may be used.
The anisotropic conductive material is used to obtain various connection structures. Examples of the connection using the anisotropic conductive material include: connection between a flexible printed Board and a Glass substrate (FOG (Film on Glass)), connection between a semiconductor Chip and a flexible printed Board (COF (Chip on Film)), connection between a semiconductor Chip and a Glass substrate (COG (Chip on Glass)), and connection between a flexible printed Board and a Glass epoxy substrate (FOB (Film on Board)).
As the conductive particles, magnetic conductive particles may be used as shown in patent documents 1 and 2 below.
Patent document 1 describes, as the conductive particles having magnetic properties, magnetic conductive particles at least a part of which is made of a magnetic material and which can be magnetized. Patent document 1 describes, as the magnetic conductive particles, gold/nickel-coated resin particles, nickel metal particles, nickel-coated resin particles containing a phosphorus element, and the like.
Patent document 2 discloses a composite material comprising a matrix and a coating layer covering the surface of the matrixConductive particles of curdlan particles. The mother particle has a plastic core body and a plating layer coating the surface of the plastic core body. The plating layer has a nickel/phosphorus alloy layer. The particle diameter of the mother particle is 2.0-3.0 μm, and the saturation magnetization of the mother particle is 45emu/cm 3 The particle diameter of the insulating sub-particles is 180nm to 500 nm.
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 2012-069255
Patent document 2: japanese patent laid-open publication No. 2013-258138
Disclosure of Invention
Technical problem to be solved by the invention
As the conductive particles, magnetic conductive particles may be used. However, in the conventional conductive particles described in patent documents 1 and 2, it is difficult to simultaneously exhibit both of the characteristics of increasing saturation magnetization and decreasing residual magnetization.
In the case of conductive particles having a low saturation magnetization, it is difficult to arrange the conductive particles between electrodes in the vertical direction to be connected to each other by a magnetic field.
In addition, in the conductive particles having a high residual magnetization, for example, magnetic aggregation of the conductive particles is likely to occur.
In addition, in conventional conductive particles having magnetic properties, it is difficult to reduce the coefficient of variation (CV value) of the particle diameter of the conductive particles. When the coefficient of variation in the particle diameter of the conductive particles is large, a short circuit may occur between electrodes in the lateral direction that should not be connected, and particularly, a short circuit may easily occur between electrodes with a fine pitch.
The invention aims to: provided are conductive particles which can improve saturation magnetization, can reduce remanent magnetization, and can improve conduction reliability when electrodes are electrically connected. Further, the present invention aims to: a conductive material and a connection structure using the conductive particles are provided.
Means for solving the problems
According to a broad aspect of the present invention, there is provided a conductive particle including a resin particle and a conductive portion disposed outside an outer surface of the resin particle, the conductive particle including the following configuration a, configuration B, or configuration C.
The structure A is as follows: the magnetic recording medium is provided with a magnetic body section comprising a magnetic body disposed between the resin particles and the conductive section, and the ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less.
The composition B is as follows: the conductive portion includes a magnetic body, and a ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less.
And C: the resin particles include a magnetic body.
In one specific aspect of the conductive particle of the present invention, the conductive particle includes the configuration a.
In one specific aspect of the conductive particle of the present invention, the conductive particle includes the structure B.
In one specific aspect of the conductive particle of the present invention, the conductive particle includes the component C.
In one specific aspect of the conductive particle of the present invention, the content of the magnetic material contained in the conductive particle is 5 vol% or more and 85 vol% or less in 100 vol% of the conductive particle.
In one specific aspect of the conductive particle of the present invention, the content of the magnetic material contained in the conductive particle is 10 wt% or more and 99 wt% or less in 100 wt% of the conductive particle.
In one specific embodiment of the conductive particles of the present invention, the particle diameter of the conductive particles is 0.1 μm or more and 1000 μm or less.
In one specific aspect of the conductive particle of the present invention, the magnetic material is a metal or a metal oxide.
In one specific aspect of the conductive particle of the present invention, the magnetic body contains iron, cobalt, ferrite, nickel, or an alloy thereof.
In one specific aspect of the conductive particle of the present invention, the conductive particle further includes: an insulating material disposed on an outer surface of the conductive portion.
In one specific aspect of the conductive particle of the present invention, the conductive particle has a protrusion on an outer surface of the conductive portion.
According to a broad aspect of the present invention, there is provided a conductive material comprising the conductive particles and a binder resin.
According to a broad aspect of the present invention, there is provided a connection structure comprising: the present invention provides a semiconductor device including a1 st connection target member having a1 st electrode on a surface thereof, a2 nd connection target member having a2 nd electrode on a surface thereof, and a connection portion connecting the 1 st connection target member and the 2 nd connection target member, wherein the connection portion is formed of conductive particles or a conductive material including conductive particles and a binder resin, the conductive particles are the conductive particles, and the 1 st electrode and the 2 nd electrode are electrically connected by the conductive particles.
Effects of the invention
The conductive particle of the present invention includes a resin particle and a conductive portion disposed outside an outer surface of the resin particle, and the conductive particle includes the following configuration a, configuration B, or configuration C. The structure A is as follows: the magnetic recording medium is provided with a magnetic body section comprising a magnetic body disposed between the resin particles and the conductive section, and the ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less. The composition B is as follows: the conductive portion includes a magnetic body, and a ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less. And C: the resin particles include a magnetic body. The conductive particles of the present invention, which have the above-described configuration, can have improved saturation magnetization and reduced residual magnetization, and can have improved conduction reliability when electrodes are electrically connected.
Drawings
Fig. 1 is a cross-sectional view schematically showing conductive particles according to embodiment 1 of the present invention.
Fig. 2 is a cross-sectional view schematically showing conductive particles according to embodiment 2 of the present invention.
Fig. 3 is a cross-sectional view schematically showing conductive particles according to embodiment 3 of the present invention.
Fig. 4 is a cross-sectional view schematically showing conductive particles according to embodiment 4 of the present invention.
Fig. 5 is a cross-sectional view schematically showing conductive particles according to embodiment 5 of the present invention.
Fig. 6 is a cross-sectional view showing an example of a connection structure using conductive particles according to embodiment 1 of the present invention.
Detailed Description
The present invention will be described in detail below.
(conductive particles)
The conductive particle of the present invention includes a resin particle and a conductive portion disposed outside an outer surface of the resin particle, and the conductive particle includes the following configuration a, configuration B, or configuration C.
The structure A is as follows: the magnetic recording medium is provided with a magnetic body section comprising a magnetic body disposed between the resin particles and the conductive section, and the ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less.
The composition B is as follows: the conductive portion contains a magnetic substance, and the ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less.
And C: the resin particles include a magnetic body.
The conductive particles of the present invention, which have the above-described configuration, can have improved saturation magnetization and reduced residual magnetization, and can have improved conduction reliability when electrodes are electrically connected.
In the conductive particles of the present invention, since saturation magnetization can be increased, even in the case of a conductive material having a high viscosity, the conductive particles contained in the conductive material can be aligned favorably between the electrodes in the vertical direction to be connected by a magnetic field.
In addition, in the conductive particles of the present invention, since the residual magnetization can be reduced, the magnetic aggregation of the conductive particles can be effectively suppressed.
In addition, the conductive particles of the present invention can improve conduction reliability. In the conductive particles of the present invention, when the electrodes are electrically connected, the connection resistance between the electrodes in the vertical direction to be connected can be effectively reduced, and the insulation reliability between the electrodes in the horizontal direction to be not connected can be improved.
The conductive particles of the present invention have at least one of the above-described configuration a, the above-described configuration B, and the above-described configuration C. The conductive particles of the present invention may include only the above-described configuration a, only the above-described configuration B, or only the above-described configuration C. The conductive particle of the present invention may have at least two of the above-described configuration a, the above-described configuration B, and the above-described configuration C. The conductive particle of the present invention may include the above-described configuration a and the above-described configuration B, may include the above-described configuration B and the above-described configuration C, or may include the above-described configuration a and the above-described configuration C. The conductive particle of the present invention may include the above-described configuration a, the above-described configuration B, and the above-described configuration C.
In the conductive particles having the configuration a or the configuration B, a ratio of residual magnetization to saturation magnetization (residual magnetization/saturation magnetization) in the conductive particles is 0.4 or less. When the ratio (residual magnetization/saturation magnetization) exceeds 0.4, magnetic agglomeration may easily occur or conduction reliability may be lowered.
In the conductive particles having the configuration a or the configuration B, the ratio of residual magnetization to saturated magnetization (residual magnetization/saturated magnetization) is preferably 0.3 or less, more preferably less than 0.1, and even more preferably less than 0.05. When the ratio (remanent magnetization/saturation magnetization) is equal to or lower than the upper limit, magnetic aggregation can be more effectively suppressed, and the on-reliability can be further improved. In the conductive particles having the configuration a or the configuration B, a ratio of residual magnetization to saturated magnetization (residual magnetization/saturated magnetization) may be 0.01 or more.
In the conductive particles having the above-described structure C, the ratio of residual magnetization to saturation magnetization (residual magnetization/saturation magnetization) is preferably 0.4 or less, more preferably 0.3 or less, still more preferably less than 0.1, and particularly preferably less than 0.05. When the ratio (remanent magnetization/saturation magnetization) is equal to or lower than the upper limit, magnetic aggregation can be more effectively suppressed, and the on-reliability can be further improved. In the conductive particles having the above-described configuration C, the ratio of residual magnetization to saturation magnetization (residual magnetization/saturation magnetization) may be 0.01 or more.
From the viewpoint of more effectively exhibiting the effects of the present invention, the residual magnetization of the conductive particles is preferably less than 2.0emu/g, more preferably 1.8emu/g or less, still more preferably 1.5emu/g or less, and particularly preferably less than 1.2emu/g. The residual magnetization of the conductive particles may be 0.5emu/g or more and may be 1.0emu/g or more.
From the viewpoint of more effectively exhibiting the effects of the present invention, the saturation magnetization of the conductive particles is preferably 15emu/g or more, more preferably 20emu/g or more, still more preferably 25emu/g or more, and particularly preferably 30emu/g or more. The conductive particles may have a saturation magnetization of 50emu/g or less.
The residual magnetization and saturation magnetization of the conductive particles can be measured using a magnetic measuring apparatus (for example, "MPMS2" manufactured by Quan tum Design Japan). Specifically, the measurement can be performed in the following manner.
The conductive particles were weighed into capsules and mounted on a sample holder. The sample holder was set in the apparatus main body, and the magnetization curve was obtained by measurement under the conditions of a temperature of 25 ℃ C (constant temperature) and a maximum applied magnetic field of 10 kOe. The residual magnetization and the saturation magnetization (emu/g) were obtained from the obtained magnetization curve.
The particle diameter of the conductive particles is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 1000 μm or less, more preferably 500 μm or less, further preferably 100 μm or less, further preferably 50 μm or less, further preferably 20 μm or less, and particularly preferably 10 μm or less. When the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes is sufficiently increased, and the conductive particles are less likely to form aggregates when forming the conductive portion. Further, the distance between the electrodes connected by the conductive particles does not become excessively large, and the conductive portion is not easily peeled off from the surface of the resin particle. When the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the conductive particles can be suitably used for the use as a conductive material.
The particle diameter of the conductive particle refers to a diameter when the conductive particle is a regular sphere, and refers to a diameter when the conductive particle is a shape other than a regular sphere, assuming a regular sphere corresponding to the volume thereof.
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 can be determined by: observing arbitrary 50 conductive particles by an electron microscope or an optical microscope, and calculating an average value of particle diameters of the conductive particles; or using a particle size distribution measuring apparatus. In observation using an electron microscope or an optical microscope, the particle diameter of each 1 conductive particle is determined as a particle diameter based on the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter based on the equivalent circle diameter and the average particle diameter based on the equivalent sphere diameter of arbitrary 50 conductive particles were approximately equal. In the particle size distribution measuring apparatus, the particle size of each 1 conductive particle was determined as a particle size based on the equivalent spherical diameter. The particle diameter of the conductive particles is preferably calculated using a particle size distribution measuring apparatus.
The coefficient of variation (CV value) of the particle diameter of the conductive particles is preferably 20% or less, more preferably 10% or less, and still more preferably 5% or less. When the coefficient of variation of the particle diameter of the conductive particles is not more than the upper limit, the conduction reliability and insulation reliability between electrodes can be further effectively improved. The coefficient of variation (CV value) of the particle diameter of the conductive particles may be 1% or more.
The coefficient of variation (CV value) can be measured in the following manner.
CV value (%) = (ρ/Dn) × 100
ρ: standard deviation of particle diameter of conductive particle
Dn: average value of particle diameter of conductive particles
The conductive particles preferably have a K value (compression modulus of elasticity at 10% compression) of 100N/mm in 10% 2 Above, more preferably 1000N/mm 2 Above, preferably 25000N/mm 2 More preferably 20000N/mm 2 The following. When the conductive particles have a 10% k value of the lower limit or more and the upper limit or less, the connection resistance between the electrodes can be more effectively reduced, the occurrence of cracks in the conductive particles can be more effectively suppressed, and the connection reliability between the electrodes can be more effectively improved.
The conductive particles preferably have a 30% K value (compression modulus of elasticity at 30% compression) of 100N/mm 2 Above, more preferably 1000N/mm 2 Above, preferably 15000N/mm 2 The concentration is preferably 10000N/mm or less 2 The following. When the 30-degree k value of the conductive particles is equal to or greater than the lower limit and equal to or less than the upper limit, the connection resistance between the electrodes can be more effectively reduced, the occurrence of cracks in the conductive particles can be more effectively suppressed, and the connection reliability between the electrodes can be more effectively improved.
The ratio of the 10-degree K value of the conductive particles to the 30-degree K value of the conductive particles (10-degree K value of conductive particles/30-degree K value of conductive particles) is preferably 1.5 or more, more preferably 1.55 or more, preferably 5 or less, more preferably 4.5 or less. When the ratio (10% k value of conductive particles/30% k value of conductive particles) is equal to or higher than the lower limit and equal to or lower than the upper limit, the connection resistance between electrodes can be more effectively reduced, the occurrence of cracks in conductive particles can be more effectively suppressed, and the connection reliability between electrodes can be more effectively improved.
The 10-percent K value and the 30-percent K value in the conductive particles can be measured in the following manner.
1 conductive particle was compressed at 25 ℃ and a compression rate of 0.3 mN/sec under a condition of a maximum test load of 20mN at a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) using a micro compression tester. The load value (N) and the compression displacement (mm) at this time were measured. The compression modulus of elasticity (10% K and 30% K) can be determined from the obtained measured values by the following equations. As the micro compression tester, a "FISCCHER SCOPE H-100" manufactured by FISCER, inc. was used. The 10-percent K-value and the 30-percent K-value of the conductive particles are preferably calculated by arithmetically averaging 10-percent K-values and 30-percent K-values of arbitrarily selected 50 conductive particles.
10% of K value and 30% of K value (N/mm) 2 )＝(3/2 1/2 )·F·S -3/2 ·R -1/2
F: load value (N) when conductive particles are compressed and deformed by 10% or 30%
S: compression displacement (mm) when conductive particles are subjected to 10% or 30% compression deformation
R: radius of conductive particle (mm)
The compressive modulus of elasticity generally and quantitatively represents the hardness of the conductive particles. By using the compressive modulus of elasticity, the hardness of the conductive particles can be quantitatively and uniquely expressed. Further, the ratio (10% k value of conductive particles/30% k value of conductive particles) can quantitatively and uniquely represent physical properties at the time of initial compression of conductive particles.
The shape of the conductive particles is not particularly limited. The conductive particles may be spherical, may be other than spherical, or may be flat.
Fig. 1 is a cross-sectional view schematically showing conductive particles according to embodiment 1 of the present invention.
The conductive particles 1 shown in fig. 1 are conductive particles having the above-described configuration a. The conductive particles 1 have: resin particles 2, a conductive part 3, and a magnetic part 4. The magnetic body 4 includes a magnetic body. The conductive portion 3 is disposed outside the outer surface of the resin particle 2. The magnetic body 4 is disposed between the resin particle 2 and the conductive part 3. Therefore, in the conductive particles 1, the magnetic portion 4 is disposed on the outer surface of the resin particle 2, and the conductive portion 3 is disposed on the outer surface of the magnetic portion 4. The conductive portion 3 is a single-layer conductive layer. The magnetic body 4 is a single-layer magnetic layer. In the conductive particles, the conductive portion may be a single-layer conductive layer, or may be a multi-layer conductive layer including 2 or more layers. In the conductive particle, the magnetic portion may be a single-layer magnetic layer, or may be a multi-layer magnetic layer including 2 or more layers.
Fig. 2 is a cross-sectional view schematically showing conductive particles according to embodiment 2 of the present invention.
The conductive particles 1A shown in fig. 2 are conductive particles having the above-described configuration B. The conductive particles 1A have: resin particles 2A, and a conductive part 3A. The conductive portion 3A includes a magnetic body. The conductive portion 3A is disposed on the outer surface of the resin particle 2A. The conductive portion 3A is a single-layer conductive layer. The conductive portion 3A is a single-layer magnetic layer. The conductive portion may be a single-layer conductive layer or a multilayer conductive layer including 2 or more layers.
Fig. 3 is a cross-sectional view schematically showing conductive particles according to embodiment 3 of the present invention.
The conductive particles 1B shown in fig. 3 are conductive particles having the above-described configuration C. The conductive particles 1B have: resin particles 2B, and a conductive part 3B. The resin particles 2B include a magnetic body 4B. The resin particles 2B enclose the magnetic body 4B. The resin particles 2B and the magnetic body 4B constitute magnetic body-encapsulated resin particles. The conductive portion 3B is disposed on the outer surface of the resin particle 2B.
Fig. 4 is a cross-sectional view schematically showing conductive particles according to embodiment 4 of the present invention.
The conductive particles 1C shown in fig. 4 are conductive particles having the above-described configuration C. The conductive particles 1C have: resin particles 2C, a conductive portion 3C, a plurality of core materials 5, and a plurality of insulating materials 6. The resin particles 2C include a magnetic substance 4C. The resin particles 2C enclose the magnetic body 4C. The resin particles 2C and the magnetic body 4C constitute magnetic body-encapsulated resin particles. The conductive portion 3C is disposed on the outer surface of the resin particle 2C so as to be in contact with the resin particle 2C. In the conductive particles, the conductive portion may be a single-layer conductive layer, or may be a multi-layer conductive layer including 2 or more layers.
The conductive particles 1C have a plurality of protrusions 1Ca on the conductive surface. The conductive portion 3C has a plurality of protrusions 3Ca on the outer surface. The plurality of core materials 5 are disposed on the surface of the resin particle 2C. The plurality of core materials 5 are embedded in the conductive portion 3C. The core material 5 is disposed inside the protrusions 1Ca, 3Ca. The conductive portion 3C covers the plurality of core materials 5. The outer surface of the conductive part 3C is raised by the plurality of core materials 5, and protrusions 1Ca and 3Ca are formed.
The conductive particles 1C have an insulating substance 6 disposed on the outer surface of the conductive portion 3C. At least a part of the outer surface of the conductive portion 3C is covered with an insulating material 6. The insulating material 6 is made of an insulating material and is insulating particles. As described above, the conductive particles of the present invention may have an insulating material disposed on the outer surface of the conductive portion. However, the conductive particles of the present invention do not necessarily have an insulating substance.
Fig. 5 is a cross-sectional view showing conductive particles according to embodiment 5 of the present invention.
The conductive particles 1D shown in fig. 5 are conductive particles having the above-described configuration a. The conductive particles 1D have: resin particles 2D, conductive portions 3D, magnetic portions 4D, a plurality of core materials 5, and a plurality of insulating materials 6.
The conductive portion 3D is disposed outside the outer surface of the resin particle 2D. The magnetic body 4D is disposed between the resin particle 2D and the conductive portion 3D. Therefore, in the conductive particles 1D, the magnetic portion 4D is disposed on the outer surface of the resin particle 2D, and the conductive portion 3D is disposed on the outer surface of the magnetic portion 4D. The conductive portion 3D is a single-layer conductive layer. The magnetic portion 4D is a single-layer magnetic layer. In the conductive particles, the conductive portion may be a single-layer conductive layer or a multilayer conductive layer including 2 or more layers. In the conductive particle, the magnetic portion may be a single-layer magnetic layer or a multi-layer magnetic layer including 2 or more layers.
The conductive particles 1D have a plurality of protrusions 1Da on the conductive surface. The conductive portion 3D has a plurality of protrusions 3Da on the outer surface. The magnetic body 4D has a plurality of projections 4Da on the outer surface. The plurality of core materials 5 are disposed on the surface of the resin particle 2D. The plurality of core materials 5 are embedded in the conductive portion 3D and the magnetic portion 4D. The core material 5 is disposed inside the protrusions 1Da, 3Da, 4Da. The magnetic body 4D covers the plurality of core materials 5. The outer surfaces of the conductive portion 3D and the magnetic portion 4D are raised by the plurality of core materials 5, and protrusions 1Da, 3Da, and 4Da are formed.
The conductive particles 1D have an insulating material 6 disposed on the outer surface of the conductive portion 3D. At least a part of the outer surface of the conductive portion 3D is covered with an insulating material 6. The insulating material 6 is made of a material having insulating properties and is insulating particles. As described above, the conductive particles of the present invention may have an insulating material disposed on the outer surface of the conductive portion. However, the conductive particles of the present invention do not necessarily have an insulating substance.
Other details of the conductive particles will be described below.
In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth) acrylic" means either or both of "acrylic" and "methacrylic".
(resin particles)
Examples of the material of the resin particles include conventionally known organic materials.
Examples of the organic material include: polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonate, polyamide, phenol-formaldehyde resin, melamine-formaldehyde resin, benzoguanamine-formaldehyde resin, urea-formaldehyde resin, phenol-formaldehyde resin, melamine resin, benzoguanamine resin, urea-formaldehyde resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyether ether ketone, polyether sulfone, divinylbenzene polymer, divinylbenzene copolymer, and the like. Examples of the divinylbenzene copolymer include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylate copolymer.
Since the compression characteristics can be easily controlled within an appropriate range, the material of the resin particles is preferably a polymer obtained by polymerizing 1 or 2 or more kinds of polymerizable monomers having an ethylenically unsaturated group.
The resin particles can be obtained by polymerizing the polymerizable monomer having the ethylenically unsaturated group. The polymerization method is not particularly limited, and examples thereof include: known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization ), addition condensation, living polymerization, and living radical polymerization. Further, another polymerization method is suspension polymerization in the presence of a radical polymerization initiator.
The particle diameter of the resin particles is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 1000 μm or less, more preferably 500 μm or less, further preferably 100 μm or less, further preferably 20 μm or less, further preferably 10 μm or less, and particularly preferably 3 μm or less. When the particle diameter of the resin particles is not less than the lower limit and not more than the upper limit, the contact area between the conductive particles and the electrode is increased, and therefore, the conduction reliability between the electrodes can be further improved, and the connection resistance between the electrodes connected by the conductive particles can be further reduced. In addition, when the conductive portion or the magnetic portion is formed on the surface of the resin particle by electroless plating, the aggregated conductive particles can be hardly formed. When the particle diameter of the resin particles is not more than the upper limit, the conductive particles are easily sufficiently compressed, the connection resistance between the electrodes can be further reduced, and the gap between the electrodes can be further reduced.
The particle diameter of the resin particle refers to a diameter when the resin particle is a regular sphere, and refers to a diameter when the resin particle is a shape other than a regular sphere, assuming a regular sphere corresponding to the volume thereof.
The particle diameter of the resin particles is preferably an average particle diameter, and more preferably a number average particle diameter. The particle size of the resin particles is determined by: observing arbitrary 50 resin particles by an electron microscope or an optical microscope, and calculating an average value of particle diameters of the resin particles; or using a particle size distribution measuring apparatus. In the observation using an electron microscope or an optical microscope, the particle diameter of each 1 resin particle is determined as a particle diameter based on the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter based on the equivalent circle diameter and the average particle diameter based on the equivalent sphere diameter of arbitrary 50 resin particles were approximately equal. In the particle size distribution measuring apparatus, the particle size of 1 resin particle was determined as the particle size based on the equivalent spherical diameter. The particle diameter of the resin particles is preferably calculated using a particle size distribution measuring apparatus. In the case of measuring the particle diameter of the resin particles in the conductive particles, the measurement can be performed, for example, in the following manner.
An embedding resin body for inspection containing conductive particles was prepared by adding the conductive particles to "TECHNOVIT4000" manufactured by Kulzer so that the content of the conductive particles was 30 wt%, and dispersing the conductive particles. The cross section of the conductive particles was cut out using an ion polishing apparatus ("IM 4000" manufactured by hitachi high and new technologies) in such a manner as to pass through the vicinity of the center of the resin particles among the conductive particles dispersed in the inspection-use embedded resin body. Then, using a field emission scanning electron microscope (FE-SEM), the resin particles in each conductive particle were observed by randomly selecting 50 conductive particles with an image magnification of 25000 times. The particle diameter of the resin particle in each conductive particle was measured and the arithmetic average was taken as the particle diameter of the resin particle.
The coefficient of variation (CV value) of the particle diameter of the resin particles is preferably 20% or less, more preferably 10% or less, and still more preferably 5% or less. When the coefficient of variation of the particle diameter of the resin particles is not more than the upper limit, the conduction reliability and insulation reliability between electrodes can be further effectively improved. The coefficient of variation (CV value) of the particle diameter of the resin particles may be 1% or more.
The coefficient of variation (CV value) can be measured in the following manner.
CV value (%) = (ρ/Dn) × 100
ρ: standard deviation of particle diameter of resin particle
Dn: average value of particle diameter of resin particles
(conductive part and magnetic body)
The conductive particles include a conductive portion disposed outside the outer surface of the resin particle. The conductive particles have the following configuration a, or configuration B or configuration C, and configuration a: a magnetic body section including a magnetic body disposed between the resin particles and the conductive section; and (B) constitution: the conductive part includes a magnetic body; and C: the resin particles include a magnetic body.
In the case where the conductive particles include the configuration a or the configuration C, the conductive portion may include a magnetic material. When the conductive particles have the configuration a, the conductive portion preferably includes a magnetic material. When the conductive particles include the structure C, the conductive portion preferably includes a magnetic body. That is, the conductive particles preferably include the configuration a and the configuration B, and preferably include the configuration B and the configuration C.
In the case where the conductive particles include the configuration a and the configuration B, the magnetic substance included in the magnetic body portion and the magnetic substance included in the conductive portion may be the same or different.
In the case where the conductive particles include the configuration B and the configuration C, the magnetic substance included in the resin particles and the magnetic substance included in the conductive portion may be the same or different.
The conductive portion preferably comprises a metal. The conductive portion may contain a substance other than metal. Hereinafter, for convenience, the metal included in the conductive portion may be referred to as "metal constituting the conductive portion". The "metal constituting the conductive portion" also includes a compound of the metal, for example, an oxide of the metal. The metal constituting the conductive portion is not particularly limited, and examples thereof include: gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, tungsten, molybdenum, alloys of these, and the like. Further, examples of the metal constituting the conductive portion include tin-doped indium oxide (ITO) and solder. The metal constituting the conductive portion may be used alone, or two or more kinds may be used in combination.
From the viewpoint of further effectively reducing the connection resistance between the electrodes, the conductive portion preferably contains nickel, gold, palladium, silver, or copper, more preferably contains nickel, gold, or palladium, and particularly preferably contains nickel.
The content of nickel in 100 wt% of the conductive portion containing nickel is preferably 10 wt% or more, more preferably 50 wt% or more, further preferably 60 wt% or more, further preferably 70 wt% or more, and particularly preferably 90 wt% or more. The content of nickel in 100 wt% of the conductive portion containing nickel may be 97 wt% or more, may be 97.5 wt% or more, may be 98 wt% or more, and may be 100 wt%.
The surface of the conductive portion often has hydroxyl groups due to oxidation. In general, a surface of a conductive portion formed of nickel is oxidized to have a hydroxyl group. The surface of the conductive portion having a hydroxyl group (surface of the conductive particle) may be provided with an insulating material by chemical bonding.
The conductive portion may be formed of one layer. The conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a stacked structure of 2 layers or more. In the case where the conductive portion is formed of a plurality of layers, the metal constituting the outermost layer is preferably an alloy containing gold, nickel, palladium, copper, or tin and silver, and more preferably gold. When the metal constituting the outermost layer is the preferable metal, the connection resistance between the electrodes is further reduced. In addition, when the metal constituting the outermost layer is gold, the corrosion resistance is further improved. The metal constituting the outermost layer may be nickel.
The thickness of the conductive portion is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, and further preferably 0.3 μm or less. When the thickness of the conductive portion is not less than the lower limit and not more than the upper limit, sufficient conductivity can be obtained, and the conductive particles are not too hard, and the conductive particles can be sufficiently deformed at the time of connection between the electrodes.
When the conductive portion is formed of a plurality of layers, the thickness of the conductive portion in the outermost layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably 0.1 μm or less. When the thickness of the outermost conductive part is not less than the lower limit and not more than the upper limit, the outermost conductive part becomes uniform, the corrosion resistance is sufficiently improved, and the connection resistance between the electrodes can be sufficiently reduced.
The thickness of the conductive portion can be measured by observing a cross section of the conductive particle using, for example, a Transmission Electron Microscope (TEM).
Magnetic body:
the magnetic body is preferably a metal or a metal oxide, and more preferably a ferromagnetic body or a paramagnetic body. The magnetic substance may be used alone or in combination of two or more.
Examples of the magnetic material include: iron, cobalt, nickel, ruthenium, lanthanides, ferrite, and the like. Examples of the ferrite include: maghemite (gamma Fe) 2 O 3 ) And MFe 2 O 4 The compound (MFe) 2 O 4 In the formula, M is Co, ni, mn, zn, mg, cu, fe, li 0.5 Fe 0.5 Etc.). The magnetic body may be an alloy. Examples of the alloy include: nickel-cobalt alloys, cobalt-tungsten alloys, iron-platinum alloys, iron-cobalt alloys, and the like. Further, the metal may be a metal ion.
From the viewpoint of further improving the magnetic collection property, the magnetic body preferably contains iron, cobalt, ferrite, nickel or an alloy thereof, more preferably contains iron, cobalt or ferrite, and still more preferably contains iron, cobalt or triiron tetroxide (Fe) 3 O 4 )。
In the conductive particles having the configuration a, the content of the magnetic material contained in the magnetic material portion is defined as a content (A1) in 100% by volume of the total of the content of the resin particles and the content of the magnetic material portion. The content (A1) is preferably 3 vol% or more, more preferably 5 vol% or more, further preferably 10 vol% or more, further preferably 15 vol% or more, further preferably 18 vol% or more, particularly preferably 20 vol% or more, preferably 45 vol% or less, more preferably 40 vol% or less, further preferably 35 vol% or less. When the content (A1) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration a, the content of the magnetic material contained in the magnetic material portion is defined as a content (A2) in 100% by weight of the total of the content of the resin particles and the content of the magnetic material portion. The content (A2) is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 30% by weight or more, further preferably 40% by weight or more, further preferably 45% by weight or more, particularly preferably 50% by weight or more, preferably 80% by weight or less, more preferably 75% by weight or less, further preferably 70% by weight or less. When the content (A2) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration a, the content of the magnetic substance contained in the conductive particles is defined as a content (A3) in 100% by volume of the conductive particles. Therefore, in the content (A3), when the conductive particles contain a magnetic body in a portion other than the magnetic portion (for example, the conductive portion or the resin particles), the content of the magnetic body also includes these. The content (A3) is preferably 2% by volume or more, more preferably 5% by volume or more, further preferably 10% by volume or more, further preferably 30% by volume or more, further preferably 35% by volume or more, particularly preferably 40% by volume or more, preferably 80% by volume or less, more preferably 75% by volume or less, further preferably 70% by volume or less. When the content (A3) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration a, the content of the magnetic substance contained in the conductive particles is defined as a content (A4) in 100% by weight of the conductive particles. Therefore, in the content (A4), when the conductive particles contain a magnetic body in a portion other than the magnetic portion (for example, the conductive portion or the resin particles), the content of the magnetic body also includes these. The content (A4) is preferably 3% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, further preferably 50% by weight or more, further preferably 70% by weight or more, particularly preferably 75% by weight or more, most preferably 80% by weight or more, preferably 97% by weight or less, more preferably 95% by weight or less. When the content (A4) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the composition B, the content of the magnetic substance contained in the conductive portion is defined as a content (B1) in 100% by volume of the total of the content of the resin particles and the content of the conductive portion. The content (B1) is preferably 3% by volume or more, more preferably 5% by volume or more, further preferably 7% by volume or more, particularly preferably 10% by volume or more, preferably 60% by volume or less, more preferably 55% by volume or less, further preferably 50% by volume or less. When the content (B1) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration B, the content of the magnetic substance contained in the conductive portion is defined as a content (B2) in 100% by weight of the total of the content of the resin particles and the content of the conductive portion. The content (B2) is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 20% by weight or more, preferably 98% by weight or less, more preferably 95% by weight or less, further preferably 90% by weight or less. When the content (B2) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration B, the content of the magnetic substance contained in the conductive particles is defined as a content (B3) in 100 vol% of the conductive particles. Therefore, in the content (B3), when the conductive particles contain magnetic bodies in portions other than the conductive portions (for example, magnetic portions or resin particles), the content of the magnetic bodies also includes these. The content (B3) is preferably 2 vol% or more, more preferably 5 vol% or more, further preferably 10 vol% or more, further preferably 15 vol% or more, further preferably 18 vol% or more, particularly preferably 20 vol% or more, preferably 95 vol% or less, more preferably 93 vol% or less, further preferably 90 vol% or less. When the content (B3) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration B, the content of the magnetic material contained in the conductive particles is defined as a content (B4) in 100% by weight of the conductive particles. Therefore, in the content (B4), when the conductive particles contain magnetic bodies in portions other than the conductive portions (for example, magnetic portions or resin particles), the content of the magnetic bodies also includes these. The content (B4) is preferably 3% by weight or more, more preferably 7% by weight or more, further preferably 10% by weight or more, further preferably 30% by weight or more, further preferably 45% by weight or more, particularly preferably 50% by weight or more, and most preferably 60% by weight or more. The content (B4) is preferably 99% by weight or less, more preferably 98% by weight or less, and further preferably 97% by weight or less. When the content (B4) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the composition C, the content of the magnetic substance contained in the resin particles is defined as a content (C1) in 100 vol% of the content of the resin particles. The content (C1) is preferably 3 vol% or more, more preferably 5 vol% or more, further preferably 10 vol% or more, further preferably 15 vol% or more, further preferably 18 vol% or more, particularly preferably 20 vol% or more, preferably 85 vol% or less, more preferably 80 vol% or less. When the content (C1) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the composition C, the content of the magnetic substance contained in the resin particles is defined as a content (C2) in 100 wt% of the content of the resin particles. The content (C2) is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 20% by weight or more, further preferably 40% by weight or more, further preferably 45% by weight or more, particularly preferably 50% by weight or more, preferably 99% by weight or less, more preferably 97% by weight or less, further preferably 95% by weight or less. When the content (C2) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration C, the content of the magnetic substance contained in the conductive particles is defined as a content (C3) in 100 vol% of the conductive particles. Therefore, in the content (C3), when the conductive particles contain a magnetic substance in a portion other than the resin particles (for example, a conductive portion or a magnetic portion), the content of the magnetic substance also includes these. The content (C3) is preferably 3 vol% or more, more preferably 7 vol% or more, further preferably 10 vol% or more, further preferably 15 vol% or more, further preferably 18 vol% or more, particularly preferably 20 vol% or more, preferably 95 vol% or less, more preferably 90 vol% or less, further preferably 88 vol% or less. When the content (C3) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles having the configuration C, the content of the magnetic substance contained in the conductive particles is defined as a content (C4) in 100% by weight of the conductive particles. Therefore, in the content (C4), when the conductive particles contain a magnetic substance in a portion other than the resin particles (for example, a conductive portion or a magnetic portion), the content of the magnetic substance also includes these. The content (C4) is preferably 3% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, further preferably 30% by weight or more, further preferably 60% by weight or more, particularly preferably 65% by weight or more, most preferably 70% by weight or more, preferably 99% by weight or less, and more preferably 97% by weight or less. When the content (C4) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles, the content of the magnetic substance contained in the conductive particles is defined as a content (D) in 100 vol% of the conductive particles. The content (D) is preferably 3 vol% or more, more preferably 5 vol% or more, further preferably 10 vol% or more, further preferably 25 vol% or more, particularly preferably 50 vol% or more, and preferably 85 vol% or less. When the content (D) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
In the conductive particles, the content of the magnetic substance contained in the conductive particles is defined as content (E) in 100 wt% of the conductive particles. The content (E) is preferably 5% by weight or more, more preferably 10% by weight or more, further preferably 15% by weight or more, further preferably 25% by weight or more, particularly preferably 40% by weight or more, preferably 99% by weight or less, more preferably 97% by weight or less. When the content (E) is not less than the lower limit and not more than the upper limit, the magnetic collection property can be further improved.
The contents (A1) to (A4), (B1) to (B4), (C1) to (C4), (D), and (E) can be measured by ICP emission spectrometry. Specifically, the measurement can be performed in the following manner.
The conductive particles are completely dissolved using hydrochloric acid or the like, and the amount of metal ions contained in the conductive particles is quantified. From the amount of the metal ions determined, the content (wt%) of the magnetic substance present in the conductive particles was calculated. Further, the volume of the magnetic body can be calculated from the density of the magnetic body. The volume of the conductive particles can be calculated from the radius of the conductive particles measured by observing the cross section of the conductive particles, and the content (volume% and weight%) of the magnetic substance can be calculated.
In the conductive particle having the above configuration a, the magnetic material portion may be a continuous layer or an aggregate layer that is an aggregate of magnetic fine particles. In the conductive particles having the configuration a, the magnetic portion is preferably an aggregate layer that is an aggregate of magnetic fine particles.
In the conductive particles having the configuration a, the primary average particle diameter of the magnetic fine particles constituting the aggregate layer which is the aggregate of the magnetic fine particles is preferably 1nm or more, more preferably 3nm or more, further preferably 5nm or more, preferably 500nm or less, more preferably 100nm or less, further preferably 50nm or less, and particularly preferably 20nm or less.
In the conductive particles having the above-described configuration C, the magnetic material preferably has a primary average particle diameter of 1nm or more, more preferably 3nm or more, further preferably 5nm or more, preferably 500nm or less, more preferably 100nm or less, further preferably 50nm or less, and particularly preferably 20nm or less.
The primary average particle diameter of the magnetic fine particles can be measured by observation using a Transmission Electron Microscope (TEM), for example.
In the case where the conductive portion of the conductive particle having the configuration a contains a magnetic material, the content of the conductive portion contained in the conductive particle is preferably 15 wt% or more, more preferably 30 wt% or more, further preferably 40 wt% or more, preferably 95 wt% or less, more preferably 85 wt% or less, and further preferably 75 wt% or less, in 100 wt% of the conductive particle. In particular, when the content of the conductive portion included in the conductive particles is not less than the lower limit and not more than the upper limit, and the primary average particle diameter of the magnetic fine particles constituting the aggregate layer is not less than the lower limit and not more than the upper limit, it is easy to adjust the ratio of residual magnetization to saturated magnetization to not more than 0.4. That is, the conductive particles having the configuration a and the configuration B can be obtained favorably.
In the conductive particles having the configuration B, the content of the conductive portion contained in the conductive particles is preferably 15% by weight or more, more preferably 30% by weight or more, further preferably 40% by weight or more, preferably 95% by weight or less, more preferably 85% by weight or less, and further preferably 75% by weight or less, in 100% by weight of the conductive particles. When the content of the conductive portion contained in the conductive particle is not less than the lower limit and not more than the upper limit, it is easy to adjust the ratio of residual magnetization to saturation magnetization to not more than 0.4. That is, the conductive particles having the above-described configuration B can be obtained satisfactorily.
In the case where the conductive portion of the conductive particle having the component C contains a magnetic substance, the content of the conductive portion contained in the conductive particle is preferably 15 wt% or more, more preferably 30 wt% or more, further preferably 40 wt% or more, preferably 95 wt% or less, more preferably 85 wt% or less, and further preferably 75 wt% or less, in 100 wt% of the conductive particle. In particular, when the content of the conductive portion included in the conductive particles is not less than the lower limit and not more than the upper limit, and the primary average particle diameter of the magnetic body is not less than the lower limit and not more than the upper limit, it is easy to adjust the ratio of residual magnetization to saturated magnetization to not more than 0.4. That is, the conductive particles having the composition C and the composition B can be obtained satisfactorily.
The content of the conductive portion contained in the conductive particles in 100 wt% of the conductive particles can be measured by energy dispersive X-ray analysis (EDX) and ICP emission spectrometry using a field emission transmission electron microscope ("JEM-2010 FEF", manufactured by japan electronics corporation). Specifically, the measurement can be performed in the following manner.
Conductive particles were added to "TECHNOVIT4000" manufactured by Kulzer, so that the content was 30 wt%, and dispersed to prepare an embedded resin body for inspection containing conductive particles. The cross section of the conductive particles was cut out using an ion polishing apparatus ("IM 4000" manufactured by hitachi high and new technologies) so as to pass through the vicinity of the center of the dispersed conductive particles embedded in the resin body for inspection. The distribution and the type of the metal contained in the conductive portion of the conductive particles can be measured by energy dispersive X-ray analysis (EDX) using a field emission transmission electron microscope ("JEM-2010 FEF" manufactured by japan electronics corporation).
The conductive particles are completely dissolved using hydrochloric acid or the like, and the amount of metal ions contained in the conductive particles is quantified. The content (wt%) of the conductive portion present in the conductive particles was calculated from the amount of the metal ions determined. Further, the volume of the conductive portion may be calculated from the density of the metal contained in the conductive portion. The volume of the conductive particles can be calculated from the radius of the conductive particles measured by observing the cross section of the conductive particles, and the content (volume% and wt%) of the conductive portion can be calculated.
In the conductive particle having the configuration a, the thickness of the magnetic portion is preferably 0.05 μm or more, more preferably 0.1 μm or more, preferably 0.5 μm or less, more preferably 0.3 μm or less, and further preferably 0.2 μm or less. When the thickness of the magnetic body portion is not less than the lower limit and not more than the upper limit, sufficient magnetic properties can be obtained and the effects of the present invention can be more effectively exhibited.
The thickness of the magnetic body can be measured by observing a cross section of the conductive particles using, for example, a Transmission Electron Microscope (TEM).
In the conductive particles having the configuration a or the configuration B, a method of forming a conductive portion or a magnetic portion on a surface of the resin particle is not particularly limited. Examples of the method for forming the conductive portion or the magnetic body portion include: a method based on electroless plating, a method based on electroplating, a method based on physical collision, a method based on mechanochemical reaction, a method based on physical vapor deposition or physical adsorption, and a method of applying metal powder or paste containing metal powder and a binder to the surface of resin particles, and the like. The method of forming the conductive portion or the magnetic body portion is preferably a method based on electroless plating, electroplating, or physical impact. Examples of the method based on physical vapor deposition include: vacuum evaporation, ion plating, ion sputtering and the like. In addition, as the method based on physical collision, for example, THETA comparator (manufactured by TOKUJU corporation) or the like is used.
In the conductive particles having the structure C, the magnetic substance may be dispersed and present in the resin particles, or may be present in a layer. In the conductive particles including the component C, the magnetic substance is preferably dispersed and present in the resin particles from the viewpoint of reducing residual magnetization.
For example, by mixing the resin particles having a porous structure with the magnetic material and introducing the magnetic material into the resin particles, the resin particles in which the magnetic material is dispersed and exists inside can be obtained. For example, the resin particles having a solid structure and the magnetic substance are mixed, the magnetic substance is coated on the outer surface of the resin particles, and then the outer surface of the magnetic substance is coated with a resin, whereby the resin particles having the magnetic substance in a layer state can be obtained.
(core material)
The conductive particles preferably have protrusions on the outer surface of the conductive portion. The conductive particles preferably have protrusions on the conductive surface. The projection is preferably plural. The conductive particles preferably have a plurality of the protrusions. An oxide film is usually formed on the surface of the electrode connected with the conductive particles. In the case of using conductive particles having protrusions on the surface of the conductive part, the oxide film can be effectively removed by the protrusions by disposing the conductive particles between the electrodes and pressing them. Therefore, the electrode and the conductive portion are further reliably brought into contact with each other, and the connection resistance between the electrodes is further reduced. In addition, when the conductive particles include an insulating material or when the conductive particles are dispersed in a binder resin and used as a conductive material, the insulating material or the binder resin between the conductive particles and the electrode can be removed more effectively due to the protrusions of the conductive particles. Therefore, the connection resistance between the electrodes can be further reduced.
Examples of the method for forming the protrusion include: a method of forming a conductive portion by electroless plating after attaching a core material to the surface of the metal particle; and a method of forming a conductive portion on the surface of the metal particle by electroless plating, then attaching the core material thereto, and then forming a conductive portion by electroless plating. Further, the protrusions may be formed without using the core material.
Other methods for forming the protrusions include: and a method of adding a core material at a stage in which a conductive portion is formed on the surface of the metal particle. Further, it is possible to use: and a method of forming a conductive portion by electroless plating after forming the conductive portion on the metal particle without using the core material, depositing the conductive portion on the surface of the conductive portion in a protruding state by plating, and then forming the conductive portion by electroless plating.
Examples of a method for adhering the core material to the surface of the metal particle include: a method in which a core material is added to a dispersion liquid of metal particles, and the core material is aggregated and attached to the surface of the metal particles by van der waals force; and a method of adding a core material to a container in which metal particles are contained, and attaching the core material to the surface of the metal particles by a mechanical action due to rotation of the container or the like. From the viewpoint of controlling the amount of the core material to be attached, the method of attaching the core material to the surface of the metal particles is preferably a method of aggregating and attaching the core material to the surface of the metal particles in the dispersion liquid.
Examples of the material constituting the core material include a conductive material and a non-conductive material. Examples of the conductive material include: conductive nonmetal such as metal, metal oxide, and graphite, and conductive polymer. Examples of the conductive polymer include polyacetylene and the like. Examples of the non-conductive substance include: silica, alumina, zirconia, and the like. From the viewpoint of further effectively removing the oxide film, the core material is preferably hard. The core material is preferably a metal from the viewpoint of further effectively reducing the connection resistance between the electrodes.
The metal is not particularly limited. Examples of the metal include: metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, and alloys of 2 or more metals such as tin-lead alloy, tin-copper alloy, tin-silver alloy, tin-lead-silver alloy, and tungsten carbide. From the viewpoint of further effectively reducing the connection resistance between the electrodes, the metal is preferably nickel, copper, silver, or gold. The metal may be the same as or different from the metal constituting the conductive portion (conductive layer). The metal may be the same as or different from the metal constituting the metal particles.
The shape of the core material is not particularly limited. The shape of the core material is preferably a block. Examples of the core material include: particulate masses, agglomerated masses in which a plurality of fine particles are agglomerated, irregular masses, and the like.
The particle diameter of the core material is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, more preferably 0.2 μm or less. When the particle diameter of the core material is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced.
The particle size of the core material is preferably an average particle size, more preferably a number average particle size. The particle size of the core material can be determined by: observing arbitrary 50 core substances by an electron microscope or an optical microscope, and calculating an average value of particle diameters of the core substances; or using a particle size distribution measuring apparatus. In the observation using an electron microscope or an optical microscope, the particle diameter of each 1 core material was determined as a particle diameter based on the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter based on the equivalent circle diameter and the average particle diameter based on the equivalent sphere diameter of any 50 core substances were approximately equal. In the case of the particle size distribution measuring apparatus, the particle size of 1 core material was determined as a particle size based on the equivalent spherical diameter. The average particle diameter of the core material is preferably calculated using a particle size distribution measuring apparatus.
The number of the protrusions per 1 conductive particle is preferably 3 or more, and more preferably 5 or more. The upper limit of the number of the protrusions is not particularly limited. The upper limit of the number of the protrusions may be appropriately selected in consideration of the particle diameter of the conductive particles and the like. When the number of the protrusions is equal to or greater than the lower limit, the connection resistance between the electrodes can be further effectively reduced.
The number of the protrusions can be calculated by observing any conductive particles with an electron microscope or an optical microscope. The number of protrusions is preferably determined by: arbitrary 50 conductive particles were observed by an electron microscope or an optical microscope, and an average value of the number of protrusions in each conductive particle was calculated.
The height of the protrusions is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, more preferably 0.2 μm or less. When the height of the protrusion is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced.
The height of the protrusions can be calculated by observing the protrusions in any of the conductive particles with an electron microscope or an optical microscope. The height of the protrusion is preferably calculated as the height of the protrusion of 1 conductive particle, which is the average of the heights of all the protrusions of 1 conductive particle. The height of the protrusion is preferably determined by: the average value of the height of the protrusions of each conductive particle was calculated for any 50 conductive particles.
(insulating Material)
The conductive particles preferably include an insulating material disposed on an outer surface of the conductive portion. In this case, when the conductive particles are used for connection between electrodes, short-circuiting between adjacent electrodes can be more effectively prevented. Specifically, when the plurality of conductive particles are brought into contact with each other, the insulating material is present between the plurality of electrodes, and therefore, short-circuiting between adjacent electrodes in the lateral direction can be prevented as well as between upper and lower electrodes. When the electrodes are connected, the insulating material between the conductive portion of the conductive particles and the electrodes can be easily removed by pressurizing the conductive particles with two electrodes. In addition, in the case of the conductive particles having the protrusions on the outer surface of the conductive portion, the insulating material between the conductive portion of the conductive particles and the electrode can be removed more easily.
The insulating material is preferably insulating particles from the viewpoint of further facilitating removal of the insulating material at the time of pressure bonding between the electrodes.
Examples of the material of the insulating material include the resin and an inorganic material. The material of the insulating material is preferably the resin. The insulating material may be used alone or in combination of two or more.
Examples of the inorganic substance include: silica, alumina, barium titanate, zirconia, carbon black, silicate glass, borosilicate glass, lead glass, soda-lime glass, alumina silicate glass, and the like.
Examples of other materials of the insulating material include: polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked products of thermoplastic resins, thermosetting resins, water-soluble resins, and the like.
Examples of the polyolefin compound include: polyethylene, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, and the like. 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 copolymers, SB-type styrene-butadiene block copolymers, SBs-type styrene-butadiene block copolymers, and hydrogenated products thereof. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. Examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin, and the like. Examples of the crosslinked product of the thermoplastic resin include introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate, and the like. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and methyl cellulose. Further, in the adjustment of the polymerization degree, a chain transfer agent may be used. Examples of the chain transfer agent include mercaptans, carbon tetrachloride and the like.
Examples of the method for disposing the insulating material on the surface of the conductive portion include a chemical method and a physical or mechanical method. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization (hybridization), electrostatic adhesion, spraying, and methods based on immersion and vacuum deposition. In the case where the electrodes are electrically connected, the method of disposing the insulating material on the surface of the conductive portion is preferably a physical method from the viewpoint of further effectively improving the insulation reliability and the conduction reliability.
The outer surface of the conductive portion and the outer surface of the insulating material may be coated with a compound having a reactive functional group. The outer surface of the conductive portion and the outer surface of the insulating material may be indirectly chemically bonded to each other through a compound having a reactive functional group without being chemically bonded to each other. After introducing a carboxyl group to the outer surface of the conductive portion, the carboxyl group may be chemically bonded to a functional group on the outer surface of the insulating material via a polymer electrolyte such as polyethyleneimine.
When the insulating material is insulating particles, the particle size of the insulating particles can be appropriately selected depending on the particle size of the conductive particles, the application of the conductive particles, and the like. The particle diameter of the insulating particles is preferably 10nm or more, more preferably 100nm or more, further preferably 300nm or more, particularly preferably 500nm or more, preferably 4000nm or less, more preferably 2000nm or less, further preferably 1500nm or less, and particularly preferably 1000nm or less. When the particle diameter of the insulating particles is not less than the lower limit, when the conductive particles are dispersed in the binder resin, the conductive portions of the plurality of conductive particles are not easily brought into contact with each other. When the particle size of the insulating particles is not more than the upper limit, it is not necessary to remove the insulating particles between the electrode and the conductive particles by excessively increasing the pressure or to remove the insulating particles between the electrode and the conductive particles by heating at a high temperature in the case of connecting the electrodes.
The particle diameter of the insulating particles is preferably an average particle diameter, and is preferably a number average particle diameter. The particle diameter of the insulating particles can be determined by: observing arbitrary 50 insulating particles by an electron microscope or an optical microscope, and calculating an average value of particle diameters of the insulating particles; or using a particle size distribution measuring apparatus. In observation with an electron microscope or an optical microscope, the particle diameter of each 1 insulating particle is determined as a particle diameter based on the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter based on the equivalent circle diameter and the average particle diameter based on the equivalent sphere diameter of arbitrary 50 insulating particles were approximately equal. In the case of the particle size distribution measuring apparatus, the particle size of 1 insulating particle is determined as a particle size based on the equivalent spherical diameter. The average particle diameter of the insulating particles is preferably calculated using a particle size distribution measuring apparatus. In the case where the particle diameter of the insulating particles is measured, the conductive particles can be measured, for example, in the following manner.
Conductive particles were added to "TECHNOVIT4000" manufactured by Kulzer, so that the content was 30 wt%, and dispersed to prepare an embedded resin body for inspection containing conductive particles. The cross section of the conductive particles was cut out by an ion mill ("IM 4000" manufactured by hitachi high-tech company) so as to pass through the vicinity of the center of the insulating particles among the conductive particles dispersed in the inspection embedded resin body. Then, using a field emission scanning electron microscope (FE-SEM), the insulating particles of each conductive particle were observed by randomly selecting 50 conductive particles with an image magnification of 5 ten thousand. The particle diameter of the insulating particles in each conductive particle was measured, and the arithmetic mean of these was taken as the particle diameter of the insulating particles.
The ratio of the particle diameter of the conductive particles to the particle diameter of the insulating particles (particle diameter of conductive particles/particle diameter of insulating particles) is preferably 4 or more, more preferably 8 or more, preferably 200 or less, and more preferably 100 or less. When the ratio (particle diameter of conductive particles/particle diameter of insulating particles) is not less than the lower limit and not more than the upper limit, insulation reliability and conduction reliability can be further effectively improved when electrodes are electrically connected.
(conductive Material)
The conductive material of the present invention contains the conductive particles and a binder resin. The conductive particles are preferably dispersed in a binder resin to serve as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive material is suitable for electrical connection of the electrodes. The conductive material is preferably a circuit connecting material.
The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. The binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component. Examples of the curable component include a photocurable component and a thermosetting component. The photocurable component preferably includes a photocurable compound and a photopolymerization initiator. The thermosetting component preferably comprises a thermosetting compound and a thermal curing agent. Examples of the binder resin include: vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, elastomers, and the like. The binder resin may be used alone or in combination of two or more.
Examples of the vinyl resin include: vinyl acetate resins, acrylic resins, styrene resins, and the like. Examples of the thermoplastic resin include: polyolefin resins, ethylene-vinyl acetate copolymers, polyamide resins, and the like. Examples of the curable resin include: epoxy resins, polyurethane resins, polyimide resins, unsaturated polyester resins, and the like. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include: styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated products of styrene-butadiene-styrene block copolymers, hydrogenated products of styrene-isoprene-styrene block copolymers, and the like. Examples of the elastomer include: styrene-butadiene copolymer rubber, acrylonitrile-styrene block copolymer rubber, and the like.
The conductive material may contain various additives such as a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, and a flame retardant in addition to the conductive particles and the binder resin.
As a method for dispersing the conductive particles in the binder resin, a conventionally known dispersion method can be used. Examples of the method of dispersing the conductive particles in the binder resin include the following methods. A method of adding the conductive particles to the binder resin, and then kneading and dispersing the mixture by a planetary mixer or the like. A method in which the conductive particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, then added to the binder resin, kneaded by a planetary mixer or the like, and dispersed. A method of diluting the binder resin with water, an organic solvent, or the like, adding the conductive particles, and kneading and dispersing the mixture by a planetary mixer or the like.
The viscosity (. Eta.25) of the conductive material at 25 ℃ is preferably 30 pas or more, more preferably 50 pas or more, preferably 400 pas or less, and more preferably 300 pas or less. When the viscosity of the conductive material at 25 ℃ is not lower than the lower limit and not higher than the upper limit, the connection reliability between electrodes can be further effectively improved. The viscosity (. Eta.25) can be suitably adjusted depending on the kind and amount of the compounding ingredients.
The viscosity (. Eta.25) can be measured at 25 ℃ and 5rpm, for example, using an E-type viscometer ("TVE 22L" manufactured by Toyobo industries, ltd.).
The conductive material can be used as a conductive paste, a conductive film, and the like. In the case where the conductive material of the present invention is a conductive film, a film containing no conductive particles may be stacked on the conductive film containing 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, further preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.99% by weight or less, more preferably 99.9% by weight or less, in 100% by weight of the conductive material. When the content of the binder resin is not less than the lower limit and not more than the upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target members connected by the conductive material is further improved.
The content of the conductive particles is preferably 0.01 wt% or more, more preferably 0.1 wt% or more, preferably 80 wt% or less, more preferably 60 wt% or less, further preferably 40 wt% or less, further preferably 20 wt% or less, and particularly preferably 10 wt% or less, in 100 wt% of the conductive material. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, and the connection reliability between the electrodes can be further effectively improved.
(connection structure and method for manufacturing connection structure)
The connection structure of the present invention includes: the first connection target member includes a1 st connection target member having a1 st electrode on a surface thereof, a2 nd connection target member having a2 nd electrode on a surface thereof, and a connection portion connecting the 1 st connection target member and the 2 nd connection target member. In the connection structure of the present invention, the connection portion is formed of conductive particles or a conductive material containing conductive particles and a binder resin, the conductive particles are the conductive particles, and the 1 st electrode and the 2 nd electrode are electrically connected by the conductive particles.
The connection structure can be obtained by the following steps: a step of disposing the conductive particles or the conductive material between the 1 st connection target member and the 2 nd connection target member, and a step of performing conductive connection by thermocompression bonding. When the conductive particles have the insulating material, the insulating material is preferably detached from the conductive particles at the time of the thermal compression.
When the conductive particles are used alone, the connection part itself is a conductive particle. That is, the 1 st connection target member and the 2 nd connection target member are connected by the conductive particles. The conductive material used for obtaining the connection structure is preferably an anisotropic conductive material.
Fig. 6 is a front cross-sectional view schematically showing a connection structure using conductive particles according to embodiment 1 of the present invention.
The connection structure 51 shown in fig. 6 includes: a1 st connection target member 52, a2 nd connection target member 53, and a connection portion 54 connecting the 1 st and 2 nd connection target members 52, 53. The connection portion 54 is formed by curing a conductive material containing the conductive particles 1. In fig. 6, 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 1A, 1B, 1C, and 1D may be used.
The method for producing the connection structure is not particularly limited. The method for manufacturing the connection structure preferably includes the following steps.
And a1 st disposing step of disposing the conductive particles or a conductive material containing the conductive particles and a binder resin on a surface of a1 st connection target member having a1 st electrode on the surface.
And a2 nd disposing step of disposing a2 nd connection target member having a2 nd electrode on a surface of the conductive particle or the conductive material opposite to the 1 st connection target member.
A step of applying a magnetic field or a magnetic force before or after the 2 nd disposing step.
In this way, a connection structure in which the 1 st electrode and the 2 nd electrode are electrically connected by the conductive particles can be obtained.
In the method for manufacturing the connection structure, it is preferable that the thermocompression bonding step is performed after the 2 nd arrangement step and after the step of applying the magnetic field or the magnetic force. A connection structure having excellent connection reliability can be obtained by thermocompression bonding the laminate of the 1 st connection object member, the conductive particles or the conductive material, and the 2 nd connection object member.
The pressure of the thermocompression bonding is preferably 40MPa or more, more preferably 60MPa or more, preferably 90MPa or less, and more preferably 70MPa or less. The heating temperature for the thermocompression bonding is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, preferably 140 ℃ or lower, and more preferably 120 ℃ or lower. When the pressure and temperature of the thermocompression bonding are not lower than the lower limit and not higher than the upper limit, the conduction reliability and insulation reliability between the electrodes can be further improved. In addition, in the case where the conductive particles have the insulating particles, the insulating particles can be easily detached from the surfaces of the conductive particles at the time of conductive connection.
In the case where the conductive particles have the insulating particles, the insulating particles present between the conductive particles and the 1 st and 2 nd electrodes can be removed when the laminate is heated and pressurized. For example, when the heating and the pressurizing are performed, the insulating particles present between the conductive particles and the 1 st electrode and the 2 nd electrode are easily detached from the surfaces of the conductive particles. In the heating and pressing, a part of the insulating particles may be detached from the surface of the conductive particles, and the surface of the conductive portion may be partially exposed. The 1 st electrode and the 2 nd electrode are in contact with the exposed portion of the surface of the conductive portion, and the 1 st electrode and the 2 nd electrode can be electrically connected by the conductive particles.
The 1 st connection object member and the 2 nd connection object member are not particularly limited. Specific examples of the 1 st connection target member and the 2 nd connection target member include: and electronic components such as a semiconductor chip, a semiconductor package, an LED chip, an LED package, a capacitor, and a diode, and electronic components such as a resin film, a printed circuit board, a flexible flat cable, a rigid flexible substrate, a glass epoxy substrate, and a glass substrate. The 1 st connection object component and the 2 nd connection object component are preferably electronic components.
Examples of the electrode provided in the connection target member include: metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes, SUS electrodes, and tungsten electrodes. When the member to be connected is a flexible printed circuit board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode. When the member to be connected is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode. When the electrode is an aluminum electrode, the electrode may be formed of only aluminum, or may be formed by laminating an aluminum layer on the surface of a metal oxide layer. Examples of the material of the metal oxide layer include: indium oxide doped with a metal element having a valence of 3, zinc oxide doped with a metal element having a valence of 3, and the like. Examples of the 3-valent metal element include: sn, al, ga, etc.
The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.
(example 1)
(1) Preparation of magnetic-body-containing resin particles
As the seed particles, polystyrene particles having an average particle diameter of 0.5 μm were prepared. 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion exchange water, and 120 parts by weight of a 5 wt% polyvinyl alcohol aqueous solution were mixed to prepare a mixed solution. After the mixture was dispersed by ultrasonic waves, the mixture was put into a separable flask and uniformly stirred.
Next, 150 parts by weight of divinylbenzene (monomer component), 2 parts by weight of 2,2' -azobis (methyl isobutyrate) (and "V-601" manufactured by Wako pure chemical industries, ltd.), and 2 parts by weight of benzoyl peroxide (NYPER BW manufactured by NOF Ltd.) were mixed. Furthermore, 9 parts by weight of triethanolamine lauryl sulfate, 50 parts by weight of toluene (solvent), and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.
The emulsion was added to the mixed solution in the separable flask, and stirred for 12 hours to allow the seed particles to absorb the monomer, thereby obtaining a suspension containing the seed particles swollen with the monomer.
Then, 490 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution was added thereto, heating was started, and the mixture was reacted at 85 ℃ for 9 hours to obtain resin particles having an average particle diameter of 2.72. Mu.m.
1 part by weight of the obtained resin particles and 10 parts by weight of 20% sulfuric acid were weighed into a 300mL beaker equipped with a stirrer, and then stirred at 200rpm, and reacted at 25 ℃ for 1 hour.
Then, 1 part by weight of the resin particles, 2 parts by weight of iron (II) chloride 4 hydrate, and 25mL of distilled water were weighed into a 200mL beaker equipped with a stirrer, and then stirred at 200rpm for 1 hour at room temperature. Subsequently, the mixture was filtered and washed with distilled water to obtain particles in which iron (II) ions were combined. Then, the particles were weighed and reacted with 4 parts by weight of 28% ammonia water (manufactured by NACALATITESQUE) at 25 ℃ for 1 hour under ultrasonic irradiation to obtain resin particles containing iron oxide as a magnetic material (resin particles with magnetic material inside).
(2) Preparation of conductive particles
The obtained resin particles containing magnetic material (magnetic material-encapsulated resin particles) were washed and dried, and then 10 parts by weight of the magnetic material-encapsulated resin particles were dispersed with an ultrasonic disperser in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution, and the solution was filtered to take out the magnetic material-encapsulated resin particles. Next, the magnetic-substance-containing resin particles were added to 100 parts by weight of a1 wt% solution of dimethylamine borane to activate the surfaces of the magnetic-substance-containing resin particles. After sufficiently washing the magnetic-material-encapsulated resin particles whose surfaces were activated with water, the resin particles were added to 500 parts by weight of distilled water and dispersed to obtain a dispersion.
Further, a nickel plating solution (pH 8.5) containing 0.35mol/L of nickel sulfate, 1.38mol/L of dimethylamine borane and 0.5mol/L of sodium citrate was prepared.
The resulting suspension was stirred at 60 ℃, and the nickel plating solution was slowly dropped into the suspension to perform electroless nickel plating. Then, the suspension was filtered to remove the particles, washed with water, and dried, thereby forming a nickel-boron conductive layer on the surface of the magnetic-substance-containing resin particles, and obtaining conductive particles having a conductive portion on the surface.
(3) Preparation of conductive Material (Anisotropic conductive paste)
The obtained conductive particles (7 parts by weight), bisphenol A-type phenoxy resin (25 parts by weight), fluorene-type epoxy resin (4 parts by weight), phenol novolac-type epoxy resin (30 parts by weight), and SI-60L (manufactured by shin-chan chemical industries, ltd.) were mixed, and the mixture was defoamed and stirred for 3 minutes to obtain a conductive material (anisotropic conductive paste).
(4) Preparation of connection Structure
A transparent glass substrate was prepared, on the upper surface of which an IZO electrode pattern (1 st electrode, vickers hardness of metal on the surface of the electrode: 100 Hv) having an L/S of 10 μm/10 μm was formed. Further, a semiconductor chip was prepared in which an Au electrode pattern (No. 2 electrode, vickers hardness 50Hv of metal on the surface of the electrode) having an L/S of 10 μm/10 μm was formed on the lower surface. The obtained anisotropic conductive paste was applied onto the transparent glass substrate so that the thickness was 30 μm, to form an anisotropic conductive paste layer. Next, the semiconductor chip is laminated on the anisotropic conductive paste layer in such a manner that the electrodes face each other. Next, magnetization treatment is performed from the upper part of the electrode. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer became 100 ℃, a pressure-heating head was placed on the upper surface of the semiconductor chip, and a pressure of 85MPa was applied to cure the anisotropic conductive paste layer at 100 ℃, to obtain a connection structure.
(example 2)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the metal species of the conductive portion was changed to Ni — B/Au.
(example 3)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the metal species of the conductive portion was changed to Ni — B/Pd.
(example 4)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the metal species of the conductive portion was changed to Ni — B/Ag.
(example 5)
The reducing agent used in the preparation of the conductive portion was changed from dimethylamine borane to sodium hypophosphite, and the concentration thereof was changed to 2.6mol/L. The content of phosphorus in the Ni plating film obtained at this time was 12 wt%. The metal species of the conductive portion was further changed to Ni-P/Au. Except for these changes, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1. The obtained Ni — P/Au layer lost the function as a magnetic material.
(example 6)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 5, except that the metal species of the conductive portion was changed to Ni — P/Pd.
(example 7)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 5, except that the metal species of the conductive portion was changed to Ni — P/Ag.
(example 8)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of iron (II) chloride · 4 hydrate added was changed from 2 parts by weight to 5 parts by weight.
(example 9)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of iron (II) chloride · 4 hydrate added was changed from 2 parts by weight to 4 parts by weight.
(example 10)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of iron (II) chloride-4 hydrate added was changed from 2 parts by weight to 3 parts by weight.
(example 11)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of the iron (II) chloride · 4 hydrate added was changed from 2 parts by weight to 1 part by weight.
(example 12)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the added iron (II) chloride-4 hydrate and 28% ammonia water were changed to cobalt sulfate-7 hydrate and dimethylamine borane.
(example 13)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the added iron (II) chloride · 4 hydrate and 28% ammonia water were changed to nickel sulfate · 6 hydrate and dimethylamine borane.
(example 14)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the added iron (II) · 4 hydrate and 28% ammonia water were changed to iron sulfate · 7 hydrate and dimethylamine borane.
(example 15)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of divinylbenzene added was changed from 150 parts by weight to 50 parts by weight.
(example 16)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of divinylbenzene added was changed from 150 parts by weight to 40 parts by weight.
(example 17)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of the magnetic material-containing resin particles added was changed from 10 parts by weight to 15 parts by weight.
(example 18)
(1) Preparation of resin particles having magnetic body
Resin particles were obtained in the same manner as in example 1, except that the solvent used in the preparation of the resin particles was changed from toluene to ethanol. The average particle size of the obtained resin particles was 2.75 μm. Next, 2.0g of the resin particles were dispersed in 40.0g of ion-exchanged water by ultrasonic waves to obtain a core particle dispersion liquid.
Subsequently, a magnetic fluid (made by FERROTEC corporation, containing Fe) was added while stirring under ultrasonic irradiation 3 O 4 Magnetic material) 8.0mL, and ultrasonic dispersion was further performed for 30 minutes. The obtained dispersion was filtered and washed with ion-exchanged water to obtain resin particles having a magnetic portion (resin particles containing a magnetic portion).
(2) Preparation of conductive particles
The obtained resin particles containing the magnetic body portion were washed and dried, and then 10 parts by weight of the resin particles containing the magnetic body portion were dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and the solution was filtered to take out the resin particles containing the magnetic body portion. Next, the resin particles containing the magnetic portion were added to 100 parts by weight of a1 wt% dimethylamine borane solution to activate the surface of the resin particles containing the magnetic portion. The resin particles having the magnetic body activated on the surface thereof were sufficiently washed with water, and then added to 500 parts by weight of distilled water to disperse the resin particles, thereby obtaining a dispersion.
Further, a nickel plating solution (pH 8.5) containing 0.35mol/L of nickel sulfate, 1.38mol/L of dimethylamine borane, and 0.5mol/L of sodium citrate was prepared.
The obtained suspension was stirred at 60 ℃ while the nickel plating solution was slowly dropped into the suspension to perform electroless nickel plating. Then, the suspension was filtered to take out the particles, and the particles were washed with water and dried to form a nickel-boron conductive layer on the surface of the resin particles containing the magnetic portion, thereby obtaining conductive particles having a conductive portion on the surface.
(3) Preparation of conductive Material (Anisotropic conductive paste)
In the same manner as in example 1, a conductive material was obtained.
(4) Preparation of connection Structure
In the same manner as in example 1, a connection structure was obtained.
(example 19)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 18, except that resin particles having an average particle diameter of 1.52 μm were used and the amount of the magnetic fluid to be added was changed to 4 mL.
(example 20)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 18, except that resin particles having an average particle diameter of 1.08 μm were used and the amount of the magnetic fluid to be added was changed to 2 mL.
(example 21)
The reducing agent used in the preparation of the conductive portion was changed from dimethylamine borane to sodium hypophosphite, and the concentration thereof was changed to 2.6mol/L. The content of phosphorus in the Ni plating film obtained in this case was 12 wt%. The metal species of the conductive portion was further changed to Ni-P/Au. Except that these changes were made, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 18. The obtained Ni — P/Au layer lost the function as a magnetic material.
(example 22)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 21, except that the metal species of the conductive portion was changed to Ni — P/Pd.
(example 23)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 21, except that the metal species of the conductive portion was changed to Ni — P/Ag.
(example 24)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of the 5 wt% polyvinyl alcohol aqueous solution added was changed from 490 parts by weight to 200 parts by weight, the amount of divinylbenzene added was changed from 150 parts by weight to 50 parts by weight, and the amount of the magnetic material-encapsulating resin particles added was changed from 10 parts by weight to 15 parts by weight.
(example 25)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of the 5 wt% polyvinyl alcohol aqueous solution added was changed from 490 parts by weight to 100 parts by weight, the amount of divinylbenzene added was changed from 150 parts by weight to 50 parts by weight, and the amount of the magnetic material-containing resin particles added was changed from 10 parts by weight to 15 parts by weight.
(example 26)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1 except that after the catalyst treatment was performed by changing the amount of divinylbenzene added from 150 parts by weight to 50 parts by weight, 1g of nickel particle slurry (average particle diameter 100 nm) was added to the dispersion over 3 minutes to obtain a suspension containing magnetic-substance-encapsulated resin particles to which a core material was attached.
(example 27)
Conductive particles were obtained in the same manner as in example 1, except that the amount of divinylbenzene added was changed from 150 parts by weight to 50 parts by weight. Using the conductive particles, conductive particles with insulating particles were prepared in the following manner.
(1) Preparation of insulating particles
A1000 mL separable flask equipped with a 4-neck separable cap, a stirring paddle, a three-way cock, a condenser and a temperature probe was charged with the following monomer composition, and then distilled water was charged so that the solid content of the following monomer composition became 10% by weight, and the mixture was stirred at 200rpm and polymerized at 60 ℃ for 24 hours under a nitrogen atmosphere. The monomer composition comprises: 360mmol of methyl methacrylate, 45mmol of glycidyl methacrylate, 20mmol of p-styryl-diethylphosphine, 13mmol of ethylene glycol dimethacrylate, 0.5mmol of polyvinylpyrrolidone and 1mmol of 2,2' -azobis {2- [ N- (2-carboxyethyl) amidino ] propane }. After the reaction, the reaction mixture was freeze-dried to obtain insulating particles (average particle diameter: 360 nm) having phosphorus atoms derived from p-styryl-diethyl-phosphine on the surface.
(2) Preparation of conductive particles with insulating particles
Dispersing the insulating particles obtained in (1) in distilled water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of the insulating particles. Further, 10g of the obtained conductive particles were dispersed in 500mL of distilled water, and 1g of a 10 wt% aqueous dispersion of insulating particles was added thereto, followed by stirring at room temperature for 8 hours. After filtering the mixture through a3 μm mesh filter, the mixture was further washed with methanol and dried to obtain conductive particles with insulating particles.
Next, in the same manner as in example 1, a conductive material and a connection structure were obtained.
(example 28)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 27, except that Ni particles (average particle diameter 100 nm) were attached to resin particles at the time of preparation of the conductive particles.
(example 29)
For the preparation of the conductive layer, a copper plating solution was prepared, which was prepared by adjusting a mixture of 200g/L copper sulfate, 150g/L ethylenediaminetetraacetic acid, 100g/L sodium gluconate, and 50g/L formaldehyde to a pH of 10.5 with ammonia. The suspension was stirred at 65 ℃ and a copper plating solution was added dropwise to perform electroless copper plating. Then, the particles were taken out by filtration, washed with water, and dried to obtain conductive particles having a copper layer. Except for this, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1.
(example 30)
A tin plating solution was prepared by adjusting a mixture solution containing 15g/L tin sulfate, 45g/L ethylenediaminetetraacetic acid and 1.5g/L phosphinic acid to pH8.5 with sodium hydroxide. Further, a reducing solution was prepared by adjusting a solution containing 5g/L of sodium borohydride to pH10.0 with sodium hydroxide. The tin plating solution is dropped to perform electroless tin plating, and then reduced by the reducing solution. Then, the particles were taken out by filtration, washed with water, and dried to obtain conductive particles having a tin layer. Except for this, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1.
(example 31)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 30, except that the amount of iron (II) chloride · 4 hydrate added was changed from 2 parts by weight to 0.5 parts by weight.
(example 32)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 18, except that Cu plating was performed when forming the conductive layer.
(example 33)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 18, except that tin plating was performed when forming the conductive layer.
(example 34)
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 33, except that the magnetic fluid was not dispersed by ultrasonic waves after addition.
Comparative example 1
(1) Preparation of resin particles
Resin particles were obtained in the same manner as in example 1, except that the solvent used in the preparation of the resin particles was changed from toluene to ethanol. The average particle diameter of the resin particles was 2.75 μm.
(2) Preparation of conductive particles
After washing and drying the obtained resin particles, 10 parts by weight of the resin particles were dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and the solution was filtered to take out the resin particles. Next, the resin particles were added to 100 parts by weight of the 1 wt% dimethylamine borane solution to activate the surfaces of the resin particles. The resin particles whose surfaces were activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water to disperse the resin particles, thereby obtaining a dispersion. Thereafter, conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1.
Comparative example 2
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in comparative example 1, except that a nickel plating solution (ph 8.5) containing 0.8mol/L of nickel sulfate, 2.0mol/L of dimethylamine borane, and 1.0mol/L of sodium citrate was prepared for the preparation of the conductive particles.
Comparative example 3
A conductive material and a connection structure were obtained in the same manner as in comparative example 1, except that nickel fine particles (average particle diameter 3.0 μm, coefficient of variation 20%) were used as the conductive particles.
Comparative example 4
The nickel fine particles used in comparative example 3 were subjected to Au plating. A conductive material and a connection structure were obtained in the same manner as in comparative example 1, except that the Au-plated nickel fine particles were used as conductive particles.
Comparative example 5
Conductive particles were obtained in the same manner as in comparative example 1. Next, using the conductive particles, conductive particles with insulating particles, a conductive material, and a connection structure were obtained in the same manner as in example 27.
Comparative example 6
Conductive particles were obtained in the same manner as in comparative example 2. Next, using the conductive particles, conductive particles with insulating particles, a conductive material, and a connection structure were obtained in the same manner as in example 27.
(evaluation)
(1) Saturation magnetization and residual magnetization of conductive particles
The saturation magnetization and residual magnetization of the conductive particles were measured in the following manner using a magnetic measuring apparatus ("MPMS 2" manufactured by Quantum Design Japan). The conductive particles were weighed into a capsule, mounted on a sample holder, the sample holder was set in the apparatus main body, and the magnetization curve was obtained by measurement under the conditions of a temperature of 25 ℃ (constant temperature) and a maximum applied magnetic field of 10 kOe. The residual magnetization and the saturation magnetization are determined from the obtained magnetization curve.
[ determination criterion of saturation magnetization ]
O ^ O: more than 30emu/g
O: 20emu/g or more and less than 30emu/g
And (delta): 15emu/g or more and less than 20emu/g
X: less than 15emu/g
[ criterion for determining residual magnetization ]
O ^ O: less than 1.2emu/g
O: 1.2emu/g or more and less than 2emu/g
And (delta): 2emu/g or more and less than 5emu/g
X: 5emu/g or more
[ criterion for determining ratio (remanent magnetization/saturation magnetization) ]
O ^ O: 0 or more and less than 0.05
O: 0.05 or more and less than 0.1
And (delta): 0.1 to 0.4 inclusive
X: over 0.4
(2) Particle diameter and coefficient of variation (CV value) of conductive particles
The particle diameters of about 100000 resin particles were measured using a particle size distribution measuring apparatus ("Multisizer 4" manufactured by BECKMAN COULTER corporation) to calculate an average value of the obtained conductive particles. Further, from the measurement results of the particle diameters of the conductive particles, the coefficient of variation (CV value) of the particle diameters of the conductive particles was calculated according to the following equation.
CV value (%) = (ρ/Dn) × 100
ρ: standard deviation of particle size of coefficient of variation
Dn: average value of coefficient of variation particle diameter
[ criterion for determining coefficient of variation ]
O: less than 5%
O: more than 5% and not more than 8%
And (delta): more than 8% and 10% or less
X: more than 10 percent
(3) Thickness of conductive part and magnetic body part
The obtained conductive particles were added to "TECHNOVIT4000" manufactured by Kulzer, so that the content was 30 wt%, and dispersed to prepare an embedding resin body for inspection. The cross section of the conductive particles was cut out by an ion mill ("IM 4000" manufactured by hitachi high-tech company) so as to be dispersed in the vicinity of the center of the conductive particles in the inspection embedded resin body.
Then, using a field emission transmission electron microscope (FE-TEM) (JEM-ARM 200F manufactured by japan electronics), the image magnification was set to 5 ten thousand times, 50 conductive particles were randomly selected, and the conductive portion and the magnetic portion of each conductive particle were observed. The thickness of the conductive portion in each conductive particle was measured, and the thickness of the conductive portion and the thickness of the magnetic portion were obtained by arithmetically averaging these thicknesses.
(4) Content of magnetic substance
The following contents were measured by the ICP emission analysis method by the above method.
Content (A1) (vol%), content (A2) (wt%): the conductive particles of the composition A contain the magnetic substance contained in the magnetic substance part in a total of 100% by volume or 100% by weight of the total of the content of the resin particles and the content of the magnetic substance part
Content (B1) (vol%), content (B2) (wt%): the conductive particles B are contained in such an amount that the content of the magnetic substance contained in the conductive part is 100% by volume or 100% by weight of the total of the content of the resin particles and the content of the conductive part
Content (C1) (vol%), content (C2) (wt%): in the conductive particles constituting C, the content of the resin particles is 100 vol% or 100 wt%, and the content of the magnetic substance contained in the resin particles
Contents (A3), (B3), (C3), (D) (vol%), contents (A4), (B4), (C4), (E) (wt%): the content of the magnetic substance contained in the conductive particles in 100% by volume or 100% by weight of the conductive particles
(5) Connection resistance value (between upper and lower electrodes)
The connection resistance between the upper and lower electrodes of each of the 20 obtained connection structures was measured by the 4-terminal method, and the average value of the connection resistance was calculated. The connection resistance can be obtained by measuring the voltage when a constant current is passed, based on the relationship of voltage = current × resistance. The connection resistance is determined by the following criteria.
[ criterion for determining connection resistance ]
O ^ O: the connection resistance is 2.0 omega or less
O: the connection resistance is more than 2.0 omega and less than 5.0 omega
And (delta): the connection resistance is more than 5.0 omega and less than 10 omega
X: the connection resistance exceeds 10 omega
(6) Incidence of short circuits
In the 20 connection structural bodies obtained in the evaluation of the connection resistance value in the above (5), the resistance value was measured by a circuit tester, and the presence or absence of leakage between adjacent electrodes was judged, and the resistance value was set to 10 8 The ratio of the connection structure of Ω or less was evaluated as the short-circuit occurrence rate.
[ criterion for determining the occurrence of short-circuit ]
○○○：0％
O ^ O: more than 0% and less than 10%
O: more than 10 percent and less than 20 percent
And (delta): more than 20 percent and less than 50 percent
X: over 50 percent
The results are shown in tables 1 to 8 below.
[ Table 1]
Figure BDA0003974755680000391
[ Table 2]
Figure BDA0003974755680000401
[ Table 3]
Figure BDA0003974755680000402
[ Table 4]
Figure BDA0003974755680000411
[ Table 5]
Figure BDA0003974755680000412
[ Table 6]
Figure BDA0003974755680000421
[ Table 7]
Figure BDA0003974755680000431
[ Table 8]
Figure BDA0003974755680000432
Description of the symbols
1. 1A, 1B, 1C, 1D … conductive particles
1Ca, 1Da … protuberance
2. 2A, 2B, 2C, 2D … resin particles
3. 3A, 3B, 3C, 3D … conductive portions
3Ca, 3Da … protrusion
4. 4D … magnetic body
4B, 4C … magnetic body
4Da … protrusion
5 … core material
6 … insulating material
51 … connecting structure
52 … part to be connected 1 st
52a … No. 1 electrode
53 … the 2 nd connection target member
53a … electrode 2
54 … connector

Claims (13)

1. An electroconductive particle comprising a resin particle and an electroconductive portion disposed outside the outer surface of the resin particle,
the conductive particles have the following structure A, structure B or structure C,
the structure A is as follows: the resin particle-containing conductive part is provided with a magnetic body part comprising a magnetic body arranged between the resin particle and the conductive part, and the ratio of residual magnetization to saturation magnetization in the conductive particle is 0.4 or less,
the composition B is as follows: the conductive portion contains a magnetic substance, and the ratio of residual magnetization to saturation magnetization in the conductive particles is 0.4 or less,
and C: the resin particles include a magnetic body.
2. The conductive particle according to claim 1, which comprises the component A.
3. The conductive particle according to claim 1 or 2, which comprises the component B.
4. The conductive particle according to any one of claims 1 to 3, which comprises the constituent C.
5. The conductive particle according to any one of claims 1 to 4,
the content of the magnetic substance contained in the conductive particles is 5 vol% or more and 85 vol% or less in 100 vol% of the conductive particles.
6. The conductive particle according to any one of claims 1 to 5,
the content of the magnetic substance contained in the conductive particles is 10 wt% or more and 99 wt% or less in 100 wt% of the conductive particles.
7. The conductive particle according to any one of claims 1 to 6,
the conductive particles have a particle diameter of 0.1 to 1000 μm.
8. The conductive particle according to any one of claims 1 to 7,
the magnetic body is metal or metal oxide.
9. The conductive particle according to any one of claims 1 to 8,
the magnetic body contains iron, cobalt, ferrite, nickel, or an alloy thereof.
10. The conductive particle according to any one of claims 1 to 9, further comprising:
an insulating material disposed on an outer surface of the conductive portion.
11. The conductive particle according to any one of claims 1 to 10, which has a protrusion on an outer surface of the conductive portion.
12. An electrically conductive material, comprising:
the conductive particle as claimed in any one of claims 1 to 11, and
a binder resin.
13. A connection structure body is provided with:
a1 st connection target member having a1 st electrode on the surface,
A2 nd connection object member having a2 nd electrode on the surface thereof, and
a connecting part for connecting the 1 st connection object member and the 2 nd connection object member,
the connecting portion is formed of conductive particles or a conductive material containing conductive particles and a binder resin,
the conductive particles according to any one of claims 1 to 11,
the 1 st electrode and the 2 nd electrode are electrically connected by the conductive particles.
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