KR20190132341A - Electroconductive particle, electroconductive material, and bonded structure - Google Patents

Abstract

The electroconductive particle which can raise conduction reliability effectively is provided. As for the electroconductive particle which concerns on this invention, the ratio with respect to the 20% K value in 25 degreeC of 20% K value in 100 degreeC is 0.85 or less, the compression recovery factor in 25 degreeC is 50% or more, 80% or less, in 100 degreeC. A first configuration having a compression recovery rate of 40% or more and 70% or less; Ratio of 20% K value at 150 ° C to 20% K value at 25 ° C is 0.75 or less, compression recovery rate at 25 ° C is 50% or more, 80% or less, compression recovery rate at 150 ° C is 25% or more, 55 2nd structure which is% or less; Alternatively, the ratio of the 20% K value at 200 ° C to the 20% K value at 25 ° C is 0.65 or less, the compression recovery rate at 25 ° C is 50% or more, 80% or less, and the compression recovery rate at 200 ° C is 20% or more. And a third configuration which is 50% or less.

Description

Electroconductive particle, electroconductive material, and bonded structure

This invention relates to the electroconductive particle which can be used, for example for the electrical connection between electrodes. Moreover, this invention relates to the electrically-conductive material and bonded structure which used the said electroconductive particle.

Anisotropic conductive materials, such as an anisotropic conductive paste and an anisotropic conductive film, are widely known. In this anisotropic conductive material, electroconductive particle is disperse | distributed in binder resin. Moreover, the electroconductive particle in which the surface of the conductive layer was insulated may be used as electroconductive particle.

The anisotropic conductive material is used to obtain various bonded structures. Examples of the connection using the anisotropic conductive material include a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), a semiconductor chip and glass The connection of a board | substrate (Chip on Glass) and the connection of a flexible printed circuit board and a glass epoxy board (FOB (Film on Board)) etc. are mentioned.

As an example of the said electroconductive particle, the following patent document 1 discloses the crosslinked polymer particle and the electroconductive particle which has a metal film on the surface of the said crosslinked polymer particle. After the said crosslinked polymer particle swells the seed particle containing polymethyl methacrylate in the emulsion containing the monomer containing the di (meth) acrylate compound represented by Formula (1), and then seed-polymerizing the said monomer. Is obtained. The compression recovery increase rate represented by the formula (2) of the crosslinked polymer particles is at least -5%.

Patent Document 2 below discloses substrate particles and conductive particles having a conductive metal layer on the surface of the substrate particles. The average particle diameter of the said substrate particle is 1.0-2.5 micrometers. The 10% K value of the said substrate particle is 3000 N / mm <2> or more. 40% K value reduction rate calculated | required by Formula (1) of the said substrate particle is 30% or more.

Japanese Patent Publication No. 2014-80484 Japanese Patent Publication No. 2013-73919

In recent years, development of various electronic devices is progressing, and the material of a board | substrate is also diversifying. For example, curved panels, flexible panels that can be bent freely, and the like have been developed. Since flexibility is required for the curved panel and the like, plastic substrates such as polyimide substrates have been studied as flexible members used for curved panels and the like instead of conventional glass substrates.

When directly mounting a semiconductor chip or the like on the plastic substrate, the plastic substrate is easily deformed, destroyed, or the like due to the pressure at the time of mounting, and thus the pressure at the time of mounting should be kept as low as possible. When the pressure at the time of mounting is low, when conductive connection between electrodes using conventional electroconductive particle is performed, since the pressure given to electroconductive particle is low, the oxide film, such as the surface of electroconductive particle and the surface of an electrode, is not excluded, It may be difficult to electrically connect between electrodes. Moreover, since the pressure given to electroconductive particle is low, electroconductive particle cannot fully be deformed and it may be difficult to fully ensure the contact area of electroconductive particle and an electrode. As a result, the connection resistance between electrodes may increase.

In addition, in a bonded structure in which electrodes are electrically conductively connected by using a conductive material containing conductive particles and a binder resin, when the binder resin is receded under a high temperature and high humidity environment, the compressed conductive particles try to return to their original shape. In operation, a phenomenon called a spring back may occur. When spring back arises, the contact area of electroconductive particle and an electrode may fall, and conduction reliability may fall.

The objective of this invention is providing the electroconductive particle which can effectively lower connection resistance and can effectively raise conduction reliability, when electrically connecting between electrodes. Moreover, the objective of this invention is providing the electrically-conductive material and bonded structure which used the said electroconductive particle.

According to a broad aspect of the present invention, the ratio of 20% K value at 100 ° C to 20% K value at 25 ° C is 0.85 or less, and the compression recovery at 25 ° C is 50% or more, 80% or less, 100 ° C. Has a first constitution of 40% or more and 70% or less, or the ratio of 20% K value at 150 ° C to 20% K value at 25 ° C is 0.75 or less, and compression recovery at 25 ° C is It is 50% or more, 80% or less, and has the 2nd structure which the compression recovery rate in 150 degreeC is 25% or more and 55% or less, or 20% K value in 25 degreeC of 20% K value in 200 degreeC. Electroconductive particle provided with the 3rd structure whose ratio with respect to 0.65 or less, compression recovery in 25 degreeC is 50% or more, 80% or less, and compression recovery rate in 200 degreeC is 20% or more and 50% or less.

In any specific aspect of the electroconductive particle which concerns on this invention, the said electroconductive particle is equipped with the said 1st structure. In this case, in the electroconductive particle which concerns on this invention, the ratio with respect to 20% K value in 25 degreeC of 20% K value in 100 degreeC is 0.85 or less, and the compression recovery factor in 25 degreeC is 50% or more and 80% or less The compression recovery rate at 100 ° C. is 40% or more and 70% or less.

In any specific aspect of the electroconductive particle which concerns on this invention, the said electroconductive particle is equipped with the said 2nd structure. In this case, in the electroconductive particle which concerns on this invention, the ratio with respect to 20% K value in 25 degreeC of 20% K value in 150 degreeC is 0.75 or less, and the compression recovery factor in 25 degreeC is 50% or more and 80% or less The compression recovery rate at 150 ° C. is 25% or more and 55% or less.

In any specific aspect of the electroconductive particle which concerns on this invention, the said electroconductive particle is equipped with the said 3rd structure. In this case, in the electroconductive particle which concerns on this invention, the ratio with respect to 20% K value in 25 degreeC of 20% K value in 200 degreeC is 0.65 or less, and the compression recovery factor in 25 degreeC is 50% or more and 80% or less The compression recovery rate at 200 ° C. is 20% or more and 50% or less.

In any specific aspect of the electroconductive particle which concerns on this invention, 20% K value in said 100 degreeC is 5000 N / mm <2> or more and 16000 N / mm <2> or less.

In any specific aspect of the electroconductive particle which concerns on this invention, 20% K value in said 150 degreeC is 4500 N / mm <2> or more and 15000 N / mm <2> or less.

In any specific aspect of the electroconductive particle which concerns on this invention, 20% K value in said 200 degreeC is 4000 N / mm <2> or more and 14000 N / mm <2> or less.

In any specific aspect of the electroconductive particle which concerns on this invention, 20% K value in said 25 degreeC is 8000 N / mm <2> or more and 20000 N / mm <2> or less.

In any specific aspect of the electroconductive particle which concerns on this invention, a particle diameter exceeds 1 micrometer.

In a specific aspect of the electroconductive particle which concerns on this invention, the said electroconductive particle is equipped with a substrate particle and the electroconductive part arrange | positioned on the surface of the said substrate particle.

In certain specific aspects of the electroconductive particle which concerns on this invention, the said substrate particle is an organic-inorganic hybrid particle.

In certain specific aspects of the electroconductive particle which concerns on this invention, the said electroconductive particle is used for the electrically conductive connection use of the electrode of the flexible member of the curved state.

According to the large situation of this invention, the electrically-conductive material containing the electroconductive particle mentioned above and binder resin is provided.

According to the broad situation of this invention, the 1st connection object member which has a 1st electrode on the surface, the 2nd connection object member which has a 2nd electrode on the surface, the said 1st connection object member, and the said 2nd connection object member The connection part which connects to is provided, The material of the said connection part is the above-mentioned electroconductive particle, or the electrically-conductive material containing the said electroconductive particle and binder resin, The said 1st electrode and the said 2nd electrode are the said electroconductive particle. The connection structure which is electrically connected by the electrically conductive part in this is provided.

In the specific aspect of the bonded structure which concerns on this invention, the said bonded structure is used as a said 1st connection object member or the said 2nd connection object member, with a flexible member and the flexible member curved.

The electroconductive particle which concerns on this invention is equipped with said 1st structure, has said 2nd structure, or has said 3rd structure. In the electroconductive particle which concerns on this invention, since said structure is provided, when electrically connecting between electrodes, connection resistance can be made low effectively and conduction reliability can be improved effectively.

1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.
It is sectional drawing which shows the electroconductive particle which concerns on 2nd Embodiment of this invention.
It is sectional drawing which shows the electroconductive particle which concerns on 3rd Embodiment of this invention.
4 is a front sectional view schematically illustrating a bonded structure using conductive particles according to a first embodiment of the present invention.

Hereinafter, the detail of this invention is demonstrated.

(Conductive particles)

The electroconductive particle which concerns on this invention is equipped with the following 1st structure, or has the following 2nd structure, or has the following 3rd structure.

1st structure: The ratio of 20% K value in 100 degreeC to 20% K value in 25 degreeC is 0.85 or less, the compression recovery rate in 25 degreeC is 50% or more, 80% or less, and the compression recovery rate in 100 degreeC It is 40% or more and 70% or less

Second constitution: The ratio of 20% K value at 150 ° C to 20% K value at 25 ° C is 0.75 or less, and the compression recovery rate at 25 ° C is 50% or more and 80% or less, and the compression recovery rate at 150 ° C. 25% or more and 55% or less

Third constitution: The ratio of 20% K value at 200 ° C to 20% K value at 25 ° C is 0.65 or less, and the compression recovery rate at 25 ° C is 50% or more and 80% or less, and the compression recovery rate at 200 ° C. 20% or more and 50% or less

The electroconductive particle which concerns on this invention is equipped with at least one of the said 1st structure, the said 2nd structure, and the said 3rd structure. The electroconductive particle which concerns on this invention may be equipped with only the said 1st structure, may be provided with only the said 2nd structure among the said 1st structure, the said 2nd structure, and the said 3rd structure, and has only the said 3rd structure It may be sufficient, may be provided with the combination of any two of the said 3 structures, and may be provided with all said 3 structures.

When the electroconductive particle which concerns on this invention is equipped with the said 1st structure, the electrically conductive connection in 70-130 degreeC can be performed favorably. When the electroconductive particle which concerns on this invention is equipped with the said 2nd structure, the electrically conductive connection in 120-180 degreeC can be performed favorably. When the electroconductive particle which concerns on this invention is equipped with the said 3rd structure, the electrically conductive connection in 170-230 degreeC can be performed favorably. When the electroconductive particle which concerns on this invention is equipped with all the structures of the said 1st structure, the said 2nd structure, and the said 3rd structure, electroconductive connection in 70-230 degreeC can be performed favorably.

In this invention, since the said structure is provided, when electrically connecting between electrodes, connection resistance can be made low effectively and conduction reliability can be improved effectively.

The electroconductive particle which concerns on this invention has a comparatively high 20% K value in 25 degreeC, and is a comparatively hard electroconductive particle in 25 degreeC. When electrically connecting between electrodes, even if the pressure applied to electroconductive particle is low, since electroconductive particle is hard at the initial stage of connection, the oxide film which exists in the surface of an electrode can be excluded, and an electrode can be electrically connected. Moreover, since the change rate with respect to the 20% K value in 25 degreeC of the 20% K value in 100 degreeC, 150 degreeC, or 200 degreeC of the electroconductive particle which concerns on this invention is comparatively high, the pressure given to electroconductive particle at the time of mounting is Even if it is low, electroconductive particle can fully be deformed and the contact area of electroconductive particle and an electrode can fully be ensured. As a result, when electrically connecting between electrodes using the electroconductive particle which concerns on this invention, the connection resistance between electrodes can be made low effectively. The 20% K value can be used as an index of hardness and deformation of the conductive particles when the pressure applied to the conductive particles is low. In this invention, when the pressure applied to electroconductive particle is low, it turned out that it is important for 20% K value to satisfy a specific relationship in order to effectively lower connection resistance between electrodes.

Moreover, the electroconductive particle which concerns on this invention has a comparatively high compression recovery rate in 25 degreeC, and the effect | action which the compressed electroconductive particle tries to return to an original shape tends to act comparatively easily. Since the 20% K value at 25 degreeC mentioned above is also comparatively high, and electroconductive particle tries to maintain the shape in the initial stage of connection, oxide film, such as the surface of an electrode, can be removed more easily, and it can electrically connect between electrodes. have. Moreover, the electroconductive particle which concerns on this invention has a comparatively low compression recovery rate in 100 degreeC, 150 degreeC, or 200 degreeC, the effect which the compressed electroconductive particle tries to return to original shape is comparatively hard to operate, and springback does not generate easily. For example, about the bonded structure which electrically connected between electrodes using the electrically-conductive material containing the electroconductive particle and binder resin which concerns on this invention, even if a binder resin falls by exposing under a high temperature, high humidity environment, The effect that an electroconductive particle tries to return to original shape hardly acts, and springback hardly arises. For this reason, the fall of the contact area of electroconductive particle and an electrode can be prevented effectively, and the conduction | electrical_connection reliability between electrodes can be improved effectively. In this invention, the conduction | electrical_connection reliability between electrodes in high temperature, high humidity environment can also be improved.

In this invention, since said structure is provided, electroconductive particle can be used suitably for the electrically conductive connection use in a curved part. When electroconductive particle is used for the electroconductive connection use in a curved part, especially the outstanding conductive reliability is exhibited effectively.

The said electroconductive particle can be used suitably for the electrode conductive connection use of a flexible member, and can be used more suitably for the electrode conductive connection use of the flexible member of the curved state. By use of the said electroconductive particle, it can use in the state which bent the flexible member, showing high conduction | reliability reliability.

As a bonded structure using a flexible member, a flexible panel etc. are mentioned. The flexible panel can be used as a curved panel. It is preferable that it is used in order to form the connection part of a flexible panel, and it is preferable that the said electroconductive particle is used in order to form the connection part of a curved panel.

In order to lower connection resistance between electrodes more effectively and to raise conduction reliability between electrodes more effectively, in this invention, 20% K value satisfy | fills a specific relationship, compression recovery rate fulfills a specific relationship, these 2 I found it important to combine the dog's configuration.

In the electroconductive particle which concerns on this invention provided with the said 1st structure, the ratio with respect to 20% K value in 25 degreeC of 20% K value in 100 degreeC is 0.85 or less. From the viewpoint of lowering the connection resistance between the electrodes more effectively, the ratio of the 20% K value at 100 ° C to the 20% K value at 25 ° C is preferably 0.5 or more, more preferably 0.55 or more, preferably Preferably it is 0.83 or less, More preferably, it is 0.80 or less.

In the electroconductive particle which concerns on this invention provided with the said 2nd structure, the ratio with respect to 20% K value in 25 degreeC of 20% K value in 150 degreeC is 0.75 or less. From the viewpoint of lowering the connection resistance between the electrodes more effectively, the ratio of the 20% K value at 150 ° C to the 20% K value at 25 ° C is preferably 0.4 or more, more preferably 0.45 or more, and is preferable. Preferably it is 0.74 or less, More preferably, it is 0.73 or less.

In the electroconductive particle which concerns on this invention provided with the said 3rd structure, the ratio with respect to 20% K value in 25 degreeC of 20% K value in 200 degreeC is 0.65 or less. From the viewpoint of lowering the connection resistance between the electrodes more effectively, the ratio of the 20% K value at 200 ° C to the 20% K value at 25 ° C is preferably 0.35 or more, more preferably 0.4 or more, preferably Preferably it is 0.64 or less, More preferably, it is 0.63 or less.

20% K value in said 100 degreeC becomes like this. Preferably it is 5000N / mm <2> or more, More preferably, it is 5500N / mm <2> or more, More preferably, it is 6000N / mm <2> or more, Preferably it is 16000N / mm <2> or less, More preferably, It is 15000 N / mm <2> or less, More preferably, it is 14500 N / mm <2> or less. If the 20% K value at the said 100 degreeC is more than the said minimum and below the said upper limit, the connection resistance between electrodes can be lowered more effectively.

20% K value in said 150 degreeC becomes like this. Preferably it is 4500N / mm <2> or more, More preferably, it is 4750N / mm <2> or more, More preferably, it is 5000N / mm <2> or more, Preferably it is 15000N / mm <2> or less, More preferably, It is 14000 N / mm <2> or less, More preferably, it is 13500 N / mm <2> or less. If 20% K value in said 150 degreeC is more than the said minimum and below the said upper limit, the connection resistance between electrodes can be lowered more effectively.

20% K value in said 200 degreeC becomes like this. Preferably it is 4000N / mm <2> or more, More preferably, it is 4250N / mm <2> or more, More preferably, it is 4500N / mm <2> or more, Preferably it is 14000N / mm <2> or less, More preferably, It is 13000 N / mm <2> or less, More preferably, it is 12500 N / mm <2> or less. If 20% K value in said 200 degreeC is more than the said minimum and below the said upper limit, the connection resistance between electrodes can be lowered more effectively.

20% K value in said 25 degreeC becomes like this. Preferably it is 8000N / mm <2> or more, More preferably, it is 8250N / mm <2> or more, More preferably, it is 8500N / mm <2> or more, Preferably it is 20000N / mm <2> or less, More preferably, It is 19000 N / mm <2> or less, More preferably, it is 18000 N / mm <2> or less. When the 20% K value at 25 ° C is above the lower limit and below the upper limit, the connection resistance between the electrodes can be lowered more effectively.

From the viewpoint of lowering the connection resistance between the electrodes more effectively, the 10% K value at 150 ° C is preferably 5750 N / mm 2 or more, more preferably 6000 N / mm 2 or more, preferably 17000 N / mm 2 or less, More preferably, it is 16000 N / mm <2> or less.

From the viewpoint of lowering the connection resistance between the electrodes more effectively, the 10% K value at 200 ° C is preferably 4750 N / mm 2 or more, more preferably 5000 N / mm 2 or more, preferably 14000 N / mm 2 or less, More preferably, it is 13000 N / mm <2> or less.

In view of lowering the connection resistance between the electrodes more effectively, the 10% K value at 25 ° C is preferably 9500 N / mm 2 or more, more preferably 10000 N / mm 2 or more, preferably 24000 N / mm 2 or less, More preferably, it is 23000 N / mm <2> or less.

10% K value (10% compressive modulus), 20% K value (20% compressive modulus), 30% K value (30% compressive modulus) at 25 ° C, 100 ° C, 150 ° C and 200 ° C of the conductive particles, and The 40% K value (40% compression modulus) can be measured as follows.

Using a micro-compression tester, at the surface of a smooth indenter end of a cylinder (diameter 100 μm, made of diamond) at 25 ° C., 100 ° C., 150 ° C. or 200 ° C., under the conditions of a compression rate of 0.33 mN / sec and a maximum test load of 20 mN. One electroconductive particle is compressed. The load value N and compression displacement (mm) at this time are measured. From the obtained measured values, 10% K value (10% compressive modulus), 20% K value (20% compressive modulus), 30% K value (30% compressive modulus) or 40% K value (40%) at each temperature Compressive elastic modulus) can be obtained by the following formula. As said microcompression tester, "Microcompression tester MCT-W200" by Shimadzu Corporation, "Fischer Scope H-100" by Fisher, "Fischer Scope HM-2000" by Fisher, etc. are used, for example. 10% K value, 20% K value, 30% K value, or 40% K value in each temperature of the said electroconductive particle is 10% K value, 20% K in each temperature of 50 electroconductive particles selected arbitrarily. It is preferable to calculate by arithmetical-averaging a value, 30% K value, or 40% K value.

10% K value, 20% K value, 30% K value or 40% K value (N / mm 2) = (3/2 ^1/2 ) · F · S ^-3 / ^2R-1 / ²

F: The load value N when the electroconductive particle 10% compressive deformation, the load value N when 20% compression deformation, the load value N when 30% compression deformation, or 40% compression deformation Load value (N)

S: When the electroconductive particle compressive deformation (mm) when 10% compression deformation, the compression displacement (mm) when 20% compression deformation, the compression displacement (mm) or 40% compression deformation when 30% compression deformation Compression displacement of mm

R: radius of conductive particles (mm)

The said K value shows the hardness of electroconductive particle universally and quantitatively. By using said K value, the hardness of electroconductive particle can be shown quantitatively and uniquely.

In the electroconductive particle which concerns on this invention, the compression recovery factor in 25 degreeC is 50% or more and 80% or less. From the viewpoint of lowering the connection resistance between the electrodes more effectively and from increasing the conduction reliability between the electrodes more effectively, the compression recovery rate at 25 ° C is preferably 51% or more, more preferably 52% or more, preferably Is 78% or less, and more preferably 75% or less.

In the electroconductive particle which concerns on this invention provided with the said 1st structure, the compression recovery factor in 100 degreeC is 40% or more and 70% or less. From the viewpoint of increasing the conduction reliability between the electrodes more effectively, the compression recovery rate at 100 ° C is preferably 41% or more, more preferably 42% or more, preferably 68% or less, and more preferably 65% or less. to be.

In the electroconductive particle which concerns on this invention provided with the said 2nd structure, the compression recovery factor in 150 degreeC is 25% or more and 55% or less. From the viewpoint of increasing the conduction reliability between the electrodes more effectively, the compression recovery at 150 ° C is preferably 26% or more, more preferably 27% or more, preferably 53% or less, and more preferably 50% or less. to be.

In the electroconductive particle which concerns on this invention provided with the said 3rd structure, the compression recovery factor in 200 degreeC is 20% or more and 50% or less. From the viewpoint of increasing the conduction reliability between the electrodes more effectively, the compression recovery rate at 200 ° C is preferably 21% or more, more preferably 22% or more, preferably 48% or less, and more preferably 45% or less. to be.

The compression recovery rate in 25 degreeC, 100 degreeC, 150 degreeC, and 200 degreeC of the said electroconductive particle can be measured as follows.

Electroconductive particle is spread | dispersed on a sample stand. About the spread | dispersed electroconductive particle, the center direction of electroconductive particle is 25 degreeC, 100 degreeC, 150 degreeC, or 200 degreeC in the smooth indenter end surface of a cylinder (diameter 100 micrometers, diamond made) using a micro compression tester. Then, one electroconductive particle is compressed under the conditions of a compression rate of 0.33 mN / sec and a maximum test load of 5 mN. Thereafter, the load is removed to the original load value (0.40 mN). The load-compression displacement between them is measured, and the compression recovery rate at each temperature can be obtained from the following equation. In addition, a load speed shall be 0.33 mN / second. As said microcompression tester, "Microcompression tester MCT-W200" by Shimadzu Corporation, "Fischer Scope H-100" by Fisher, "Fischer Scope HM-2000" by Fisher, etc. are used, for example.

Compression recovery rate (%) = [L2 / L1] × 100

L1: Compression displacement from the origin load value to the reverse load value when applying the load

L2: Unloading displacement from the reverse load value to the origin load value when releasing the load

The particle diameter of the said electroconductive particle becomes like this. Preferably it is 1 micrometer or more, More preferably, it exceeds 1 micrometer, More preferably, it is 2 micrometers or more, More preferably, it exceeds 2.5 micrometers, Especially preferably, it is 3 micrometers. That's it. The particle diameter of the said electroconductive particle becomes like this. Preferably it is 1000 micrometers or less, More preferably, it is 100 micrometers or less, More preferably, it is 40 micrometers or less, Especially preferably, it is 5 micrometers or less, Most preferably, it is 2.75 micrometers or less. When the particle diameter of the said electroconductive particle is more than the said minimum and below the said upper limit, connection resistance between electrodes can be made more effectively low, and the conduction | electrical_connection reliability between electrodes can be raised more effectively. If the particle diameter of the said electroconductive particle is 1 micrometer or more and 5 micrometers or less, it can use suitably for an electrically conductive connection use.

It is preferable that it is an average particle diameter, and, as for the particle diameter of the said electroconductive particle, it is more preferable that it is a number average particle diameter. The particle diameter of the said electroconductive particle observes 50 arbitrary electroconductive particles with an electron microscope or an optical microscope, for example, calculates an average value, and calculates the average value of the measurement result by the several times laser diffraction type particle size distribution measuring apparatus. Obtained by

Although the variation coefficient of the particle diameter of the said electroconductive particle is so preferable that it is low, it is usually 0.1% or more, Preferably it is 10% or less, More preferably, it is 8% or less, More preferably, it is 5% or less. When the particle diameter variation coefficient of the said electroconductive particle is more than the said minimum and below the said upper limit, conduction | electrical_connection reliability can be improved further. However, less than 5% of the variation coefficient of the particle diameter of the said electroconductive particle may be sufficient.

The variation coefficient (CV value) can be measured as follows.

CV value (%) = (ρ / Dn) × 100

ρ: standard deviation of the particle diameter of the conductive particles

Dn: average value of particle diameters of conductive particles

The shape of the said electroconductive particle is not specifically limited. The shape of the said electroconductive particle may be spherical, and shapes other than spherical shapes, such as a flat shape, may be sufficient.

It is preferable that the said electroconductive particle is equipped with a substrate particle and the electroconductive part arrange | positioned on the surface of the said substrate particle from a viewpoint of lowering connection resistance between electrodes more effectively, and a viewpoint of raising conduction reliability between electrodes more effectively. When the said electroconductive particle is equipped with a substrate particle and the electroconductive part arrange | positioned on the surface of the said substrate particle, 20% K value satisfy | fills a specific relationship, compression recovery rate satisfy | fills a specific relationship, and satisfies these two structures. Electroconductive particle to say can be obtained easily. The electroconductive particle which satisfy | fills the said structure can be obtained by suitably adjusting the superposition | polymerization conditions of the substrate particle, and the hardness of an electroconductive part.

For the substrate particles, for example, when the substrate particles are inorganic particles or organic inorganic hybrid particles other than the metals described later, condensation is performed by adjusting the condensation reaction conditions, oxygen partial pressure during firing, firing temperature and firing time. At the time of reaction, radical polymerization reaction can be performed in a baking process, suppressing radical polymerization reaction. As a result, the substrate particle which can obtain the electroconductive particle which satisfy | fills the said structure can be obtained easily.

As for the conductive portion, by appropriately adjusting the metal species, which is a material of the conductive portion, and the thickness of the conductive portion, the physical properties of the conductive particles can obtain desired physical properties in addition to those of the substrate particles. As said metal species, the material containing nickel is mentioned as a preferable example.

Next, specific embodiment of this invention is described, referring drawings. In addition, this invention is not limited only to the following embodiment, The following embodiment may be suitably changed, improved, etc. to the extent which does not impair the characteristic of this invention.

1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.

The electroconductive particle 1 shown in FIG. 1 has the substrate particle 2 and the electroconductive part 3. The electroconductive part 3 is arrange | positioned on the surface of the substrate particle 2. In the electroconductive particle 1, the electroconductive part 3 is in contact with the surface of the substrate particle 2. The electroconductive part 3 has covered the surface of the substrate particle 2. The electroconductive particle 1 is a coating particle by which the surface of the substrate particle 2 was coat | covered with the electroconductive part 3. In the electroconductive particle 1, the electroconductive part 3 is a single-layer electroconductive part (conductive layer).

The electroconductive particle 1 is different from the electroconductive particle 11 and 21 mentioned later, and does not have a core substance. The electroconductive particle 1 does not have a processus | protrusion on the surface of electroconductivity, and does not have a processus | protrusion on the outer surface of the electroconductive part 3. The electroconductive particle 1 is spherical.

Thus, the electroconductive particle which concerns on this invention does not need to have a processus | protrusion on the surface of electroconductivity, does not need to have a processus | protrusion on the outer surface of an electroconductive part, and may be spherical. In addition, the electroconductive particle 1 is different from the electroconductive particle 11 and 21 mentioned later, and does not have an insulating substance. However, the electroconductive particle 1 may have the insulating substance arrange | positioned on the outer surface of the electroconductive part 3.

It is sectional drawing which shows the electroconductive particle which concerns on 2nd Embodiment of this invention.

The electroconductive particle 11 shown in FIG. 2 has the substrate particle 2, the electroconductive part 12, the some core material 13, and the some insulating material 14. As shown in FIG. The electroconductive part 12 is arrange | positioned on the surface of the substrate particle 2. The plurality of core materials 13 are disposed on the surface of the substrate particle 2. The electroconductive part 12 is arrange | positioned on the surface of the base material particle 2 so that the base material particle 2 and the some core substance 13 may be covered. In the electroconductive particle 11, the electroconductive part 12 is a single conductive part (electric conductive layer).

The electroconductive particle 11 has the some processus | protrusion 11a in the outer surface. In the electroconductive particle 11, the electroconductive part 12 has some protrusion 12a in the outer surface. The plurality of core materials 13 are raised on the outer surface of the conductive portion 12. As the outer surface of the conductive portion 12 is raised by the plurality of core materials 13, the protrusions 11a and 12a are formed. The plurality of core materials 13 are embedded in the conductive portion 12. The core substance 13 is arrange | positioned inside the protrusions 11a and 12a. In the electroconductive particle 11, in order to form the projection 11a and 12a, the some core substance 13 is used. In the said electroconductive particle, in order to form the said process, it is not necessary to use some said core substance. In the said electroconductive particle, it does not need to be equipped with several said core substance.

The electroconductive particle 11 has the insulating substance 14 arrange | positioned on the outer surface of the electroconductive part 12. As shown in FIG. At least a portion of the outer surface of the conductive portion 12 is covered with the insulating material 14. The insulating material 14 is formed of an insulating material and is insulating particles. Thus, the electroconductive particle which concerns on this invention may have the insulating substance arrange | positioned on the outer surface of an electroconductive part. However, the electroconductive particle which concerns on this invention does not necessarily need to have an insulating substance.

It is sectional drawing which shows the electroconductive particle which concerns on 3rd Embodiment of this invention.

The electroconductive particle 21 shown in FIG. 3 has the substrate particle 2, the electroconductive part 22, the some core material 13, and the some insulating material 14. As shown in FIG. The electroconductive part 22 as a whole has the 1st electroconductive part 22A on the substrate particle 2 side, and the 2nd electroconductive part 22B on the opposite side to the substrate particle 2 side.

The electroconductive particle 11 and the electroconductive particle 21 differ only in an electroconductive part. That is, in the electroconductive particle 11, while the electroconductive part of one layer structure is formed, in electroconductive particle 21, the 1st electroconductive part 22A and the 2nd electroconductive part 22B of a two layer structure are formed, have. The first conductive portion 22A and the second conductive portion 22B may be formed as different conductive portions, or may be formed as the same conductive portion.

22 A of 1st electroconductive parts are arrange | positioned on the surface of the substrate particle 2. The first conductive portion 22A is disposed between the substrate particle 2 and the second conductive portion 22B. The first conductive portion 22A is in contact with the substrate particle 2. The second conductive portion 22B is in contact with the first conductive portion 22A. 22 A of 1st electroconductive parts are arrange | positioned on the surface of the substrate particle 2, and the 2nd electroconductive part 22B is arrange | positioned on the surface of the 1st electroconductive part 22A.

The electroconductive particle 21 has the some processus | protrusion 21a in the outer surface. In the electroconductive particle 21, the electroconductive part 22 has some protrusion 22a in the outer surface. The first conductive portion 22A has a protrusion 22Aa on its outer surface. The second conductive portion 22B has a plurality of protrusions 22Ba on its outer surface. In the electroconductive particle 21, the electroconductive part 22 is two electroconductive parts (conductive layer). The conductive portion 22 may be two or more conductive portions.

Hereinafter, the other detail of electroconductive particle is demonstrated. In addition, in the following description, "(meth) acryl" means one or both of "acryl" and "methacryl", and "(meth) acrylate" is in "acrylate" and "methacrylate". Means one or both.

Substrate Particles:

Examples of the substrate particles include inorganic particles other than resin particles and metal particles, organic inorganic hybrid particles, metal particles, and the like. It is preferable that the said substrate particle is a substrate particle except a metal particle, and it is more preferable that it is an inorganic particle or organic inorganic hybrid particle except a resin particle and a metal particle. The said substrate particle may be core shell particle | grains provided with a core and the shell arrange | positioned on the surface of this core.

It is more preferable that the said substrate particle is a resin particle or organic inorganic hybrid particle, a resin particle may be sufficient as it, and organic inorganic hybrid particle may be sufficient as it. By use of these preferable substrate particles, the effect of this invention is exhibited more effectively, and the electroconductive particle more suitable for the electrical connection between electrodes is obtained.

When connecting between electrodes using the said electroconductive particle, after arrange | positioning the said electroconductive particle between electrodes, the said electroconductive particle is compressed by crimping | bonding. When the substrate particle is a resin particle or an organic inorganic hybrid particle, the conductive particles are easily deformed at the time of the pressing, and the contact area between the conductive particles and the electrode becomes large. For this reason, the conduction | electrical_connection reliability between electrodes becomes still higher.

As a material of the said resin particle, various resin is used suitably. As a material of the said resin particle, For example, Polyolefin resin, such as polyethylene, a polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, polybutadiene; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Polyalkyltelephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, Epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyether ether ketone, polyether sulfone and various polymerizable monomers having ethylenically unsaturated groups The polymer etc. which are obtained by superposing | polymerizing 1 type or 2 or more types are mentioned.

Since the resin particle which has the physical property at the time of arbitrary compression suitable for a electrically-conductive material can be designed and synthesize | combined, and the hardness of a base material particle can be easily controlled to a suitable range, the material of the said resin particle has a plurality of ethylenically unsaturated groups. It is preferable that it is a polymer which polymerized 1 type (s) or 2 or more types of the polymerizable monomers which have.

When obtaining the said resin particle by superposing | polymerizing the polymerizable monomer which has an ethylenically unsaturated group, as a polymerizable monomer which has the said ethylenically unsaturated group, a non-crosslinkable monomer and a crosslinkable monomer are mentioned.

As said non-crosslinkable monomer, For example, Styrene-type monomers, such as styrene and (alpha) -methylstyrene; Carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid and maleic anhydride; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) Alkyl (meth) acrylate compounds, such as an acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; Oxygen atom-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate; Nitrile-containing monomers such as (meth) acrylonitrile; Acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; And halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene.

As said crosslinkable monomer, tetramethylol methane tetra (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylol propane tri (meth) acryl, for example. Latent, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylic Polyfunctional (meth) acrylate compounds such as late, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate; Triallyl (iso) cyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene And silane-containing monomers such as vinyltrimethoxysilane.

The said resin particle can be obtained by polymerizing the polymerizable monomer which has the said ethylenically unsaturated group by a well-known method. As this method, the method of suspension polymerization in presence of a radical polymerization initiator, and the method of swelling and superposing | polymerizing a monomer with a radical polymerization initiator using a non-crosslinked seed particle, etc. are mentioned, for example.

When the said substrate particle is an inorganic particle except organic particle | grains, or an organic inorganic hybrid particle, as an inorganic substance which is a material of the said substrate particle, silica, alumina, barium titanate, zirconia, carbon black, etc. are mentioned. It is preferable that the said inorganic substance is not a metal. Although it does not specifically limit as particle | grains formed with the said silica, For example, after hydrolyzing the silicon compound which has 2 or more of hydrolysable alkoxysilyl groups, and forming a crosslinked polymer particle, the particle obtained by baking as needed is mentioned. Can be. As said organic inorganic hybrid particle | grain, organic inorganic hybrid particle | grains formed with the bridge | crosslinked alkoxysilyl polymer and acrylic resin etc. are mentioned, for example.

It is preferable that the said organic inorganic hybrid particle is a core-shell organic inorganic hybrid particle which has a core and the shell arrange | positioned on the surface of this core. It is preferable that the said core is an organic core. It is preferred that the shell is an inorganic shell. From the viewpoint of lowering the connection resistance between the electrodes more effectively, the substrate particles are preferably organic inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.

As a material of the said organic core, the material of the resin particle mentioned above, etc. are mentioned.

As a material of the said inorganic shell, the inorganic material mentioned as a material of the base material particle mentioned above is mentioned. It is preferable that the material of the said inorganic shell is silica. It is preferable that the said inorganic shell is formed by baking a said shell-like thing, after making a metal alkoxide into a shell-like thing by the sol-gel method on the surface of the said core. It is preferable that the said metal alkoxide is a silane alkoxide. It is preferable that the said inorganic shell is formed of silane alkoxide.

When the said substrate particle is a metal particle, silver, copper, nickel, silicon, gold, titanium, etc. are mentioned as a metal which is a material of this metal particle. However, it is preferable that the said substrate particle is not a metal particle.

The particle diameter of the said substrate particle becomes like this. Preferably it is 1 micrometer or more, More preferably, it is 2 micrometers or more, More preferably, it exceeds 2.5 micrometers, Especially preferably, it is 3 micrometers or more, Preferably it is 1000 micrometers or less, More Preferably it is 100 micrometers or less, More preferably, it is 40 micrometers or less, Especially preferably, it is 5 micrometers or less. If the particle diameter of the said substrate particle is more than the said minimum, since the contact area of electroconductive particle and an electrode will become large, the conduction | electrical_connection reliability between electrodes becomes still higher, and the connection resistance between the electrodes connected through electroconductive particle can be lowered more effectively. . Moreover, when forming an electroconductive part in the surface of a substrate particle, it becomes difficult to aggregate and it becomes difficult to form aggregated electroconductive particle. If the particle diameter of the said substrate particle is below the said upper limit, electroconductive particle will be easy to fully compress, and the connection resistance between the electrodes connected through electroconductive particle can be lowered more effectively. Moreover, even if the space | interval between electrodes becomes small and thickness of an electroconductive part is made thick, small electroconductive particle is obtained.

The particle diameter of the said substrate particle shows a diameter when a substrate particle is a spherical shape, and shows a maximum diameter, when a substrate particle is not a spherical shape.

The particle diameter of the said substrate particle shows a number average particle diameter. The particle diameter of the said substrate particle is calculated | required using a particle size distribution measuring apparatus etc. It is preferable that the particle diameter of a substrate particle is calculated | required by observing 50 arbitrary substrate particles with an electron microscope or an optical microscope, and calculating an average value. In electroconductive particle, when measuring the particle diameter of the said substrate particle, it can measure as follows, for example.

It adds to "techno beet 4000" made by Kulzer company, and makes it disperse | distribute so that content of electroconductive particle may be 30 weight%, and embedding resin for electroconductive particle inspection is produced. The cross section of electroconductive particle is cut out using an ion milling apparatus ("IM4000" by Hitachi High-Technologies Corporation) so that the center vicinity of the electroconductive particle dispersed in the embedding resin for inspection may be passed. And an image magnification is set to 25000 times using a field emission scanning electron microscope (FE-SEM), 50 electroconductive particles are selected at random, and the substrate particle of each electroconductive particle is observed. The particle diameter of the substrate particle in each electroconductive particle is measured, they are arithmetically averaged, and it is set as the particle diameter of a substrate particle.

Challenge:

The metal which is a material of the said electroconductive part is not specifically limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon and these And alloys thereof. Moreover, as said metal, tin dope indium oxide (ITO), a solder, etc. are mentioned. Since the connection resistance between electrodes becomes still lower, the alloy containing tin, nickel, palladium, copper, or gold is preferable, and nickel or palladium is preferable.

Moreover, since conduction | relief reliability can be improved effectively, it is preferable that the said electroconductive part and the outer surface part of the said electroconductive part contain nickel. Content of nickel in 100 weight% of conductive parts containing nickel becomes like this. Preferably it is 10 weight% or more, More preferably, it is 50 weight% or more, More preferably, it is 60 weight% or more, More preferably, it is 70 weight% or more Especially preferably, it is 90 weight% or more. The content of nickel in 100% by weight of the conductive portion containing nickel may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.

In addition, hydroxyl groups are often present on the surface of the conductive portion by oxidation. In general, hydroxyl groups exist on the surface of the conductive portion formed of nickel by oxidation. An insulating substance can be arrange | positioned through the chemical bond on the surface (surface of electroconductive particle) which has such a hydroxyl group.

Like the electroconductive particle 1 and 11, the said electroconductive part may be formed by one layer. Like the electroconductive particle 21, the electroconductive part may be formed by the some layer. That is, the electroconductive part may have a laminated structure of two or more layers. In the case where the conductive portion is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and more preferably a gold layer. When outermost layer is these preferable electroconductive part, the connection resistance between electrodes can be made low more effectively. Moreover, when outermost layer is a gold layer, corrosion resistance can be improved more effectively.

The method of forming the said electroconductive part on the surface of the said substrate particle is not specifically limited. As the method for forming the conductive portion, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a paste containing a metal powder or a metal powder and a binder on the surface of the substrate particle The method etc. are mentioned. Since formation of an electroconductive part is easy, the method by electroless plating is preferable. As said method by physical vapor deposition, methods, such as vacuum deposition, ion plating, and ion sputtering, are mentioned.

The thickness of the said electroconductive part becomes like this. Preferably it is 0.005 micrometer or more, More preferably, it is 0.01 micrometer or more, Preferably it is 10 micrometers or less, More preferably, it is 1 micrometer or less, More preferably, it is 0.3 micrometer or less. If the thickness of the said electroconductive part is more than the said minimum and below the said upper limit, sufficient electroconductivity will be obtained, electroconductive particle will not become hard too much, and electroconductive particle will fully deform | transform at the time of connection between electrodes.

In the case where the conductive portion is formed of a plurality of layers, the thickness of the conductive portion of the outermost layer is preferably 0.001 µm or more, more preferably 0.01 µm or more, preferably 0.5 µm or less, and more preferably 0.1 It is micrometer or less. If the thickness of the electrically conductive part of the outermost layer is more than the said minimum and below the said upper limit, the coating | cover by the electrically conductive part of an outermost layer becomes uniform, corrosion resistance will become high enough, and the connection resistance between electrodes will become low enough.

The thickness of the said electroconductive part can be measured by observing the cross section of electroconductive particle, for example using a transmission electron microscope (TEM).

Core material:

It is preferable that the said electroconductive particle has a some processus | protrusion on the outer surface of the said electroconductive part. When the said electroconductive particle has a some processus | protrusion on the outer surface of the said electroconductive part, the conduction | electrical_connection reliability between electrodes can be improved further. The oxide film is formed in the surface of the electrode connected by the said electroconductive particle in many cases. Moreover, the oxide film is formed in the surface of the electroconductive part of the said electroconductive particle in many cases. By using the electroconductive particle which has the said processus | protrusion, after arrange | positioning electroconductive particle between electrodes, an oxide film is effectively excluded by a processus | protrusion by crimping | bonding. For this reason, an electrode and electroconductive particle can be contacted more reliably, and the connection resistance between electrodes can be lowered more effectively. In addition, when the said electroconductive particle has an insulating substance on the surface, or when electroconductive particle is disperse | distributed in binder resin and used as a conductive material, resin between electroconductive particle and an electrode is effectively excluded by protrusion of electroconductive particle. For this reason, the conduction | electrical_connection reliability between electrodes can be raised more effectively.

By embedding the core material in the conductive portion, a plurality of protrusions can be easily formed on the outer surface of the conductive portion. However, in order to form a processus | protrusion on the surface of the electroconductive part of electroconductive particle, you do not necessarily need to use a core substance.

As a method of forming the protrusions, the core material is attached to the surface of the substrate particles, and then the conductive material is formed by electroless plating, and the conductive material is formed on the surface of the substrate particles by electroless plating. The method of adhering these and further forming a conductive part by electroless plating, etc. are mentioned. As another method of forming the projections, after forming the first conductive portion on the surface of the substrate particle, a method of disposing a core material on the first conductive portion, and then forming the second conductive portion, and the substrate particle In the middle of forming a conductive portion (such as a first conductive portion or a second conductive portion) on the surface of the substrate, a method of adding a core substance may be mentioned. In addition, in order to form a protrusion, without using the said core substance, after forming an electroconductive part by electroless-plating to a substrate particle, plating is deposited on a protrusion on the surface of an electroconductive part, and further electroless-plating is carried out. You may use the method etc. which form an electroconductive part.

As a method of arranging a core substance on the outer surface of the said substrate particle, a core substance is added to the dispersion liquid of a substrate particle, for example, a core substance is integrated by the van der Waals force etc. on the surface of a substrate particle, and it adheres, The core material is added to the container which put the substrate particle, and the method of making a core material adhere to the surface of a substrate particle by the mechanical action by rotation of a container, etc. are mentioned. Since the quantity of the core substance to adhere is easy to control, the method of integrating and attaching a core substance to the surface of the substrate particle in a dispersion liquid is preferable.

The material of the said core substance is not specifically limited. As a material of the said core substance, an electroconductive substance and a nonelectroconductive substance are mentioned, for example. Examples of the conductive material include metals, metal oxides, conductive nonmetals such as graphite, conductive polymers, and the like. Polyacetylene etc. are mentioned as said conductive polymer. Examples of the nonconductive substance include silica, alumina, barium titanate, zirconia, and the like. Since electroconductivity can be raised and connection resistance can be made low effectively, a metal is preferable. It is preferable that the said core substance is a metal particle. As a metal which is a material of the said core substance, the metal quoted as a material of the said electrically-conductive material can be used suitably.

It is preferable that Mohs' Hardness of the material of the said core substance is high. Examples of materials having high Mohs hardness include barium titanate (Moss hardness 4.5), nickel (Moss hardness 5), silica (silicon dioxide, Mohs hardness 6 to 7), titanium oxide (Moss hardness 7), and zirconia (Moss hardness 8 to 9). ), Alumina (Moss hardness 9), tungsten carbide (Moss hardness 9), diamond (Moss hardness 10), etc. are mentioned. The core material is preferably nickel, silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond, and more preferably silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond. The core material is more preferably titanium oxide, zirconia, alumina, tungsten carbide or diamond, and particularly preferably zirconia, alumina, tungsten carbide or diamond. The material Mohs' Hardness of the said core substance becomes like this. Preferably it is four or more, More preferably, it is five or more, More preferably, it is six or more, More preferably, it is seven or more, Especially preferably, it is 7.5 or more.

The shape of the said core substance is not specifically limited. It is preferable that the shape of a core substance is block shape. Examples of the core substance include particulate lumps, aggregated lumps in which a plurality of fine particles are aggregated, irregular lumps, and the like.

The particle diameter of the said core substance becomes like this. Preferably it is 0.001 micrometer or more, More preferably, it is 0.05 micrometer or more, Preferably it is 0.9 micrometer or less, More preferably, it is 0.2 micrometer or less. If the particle diameter of the said core substance is more than the said minimum and below the said upper limit, the connection resistance between electrodes will become low effectively.

The particle diameter of the said core substance shows the number average particle diameter. It is preferable to calculate | require the particle diameter of a core substance by observing 50 arbitrary core substances with an electron microscope or an optical microscope, and calculating an average value.

The number of said protrusions per said electroconductive particle becomes like this. Preferably it is three or more, More preferably, it is five or more. The upper limit of the number of the said projections is not specifically limited. The upper limit of the number of the said projections can be suitably selected considering the particle diameter of electroconductive particle, the use of electroconductive particle, etc.

It is preferable to calculate | require the number of said protrusions per said electroconductive particle by observing 50 arbitrary electroconductive particles with an electron microscope or an optical microscope, and calculating an average value.

The height of the plurality of protrusions is preferably 0.001 µm or more, more preferably 0.05 µm or more, preferably 0.9 µm or less, and still more preferably 0.2 µm or less. If the height of the said projection is more than the said minimum and below the said upper limit, the connection resistance between electrodes will become low effectively.

It is preferable to calculate | require the height of the some processus | protrusion by observing 50 arbitrary electroconductive particles with an electron microscope or an optical microscope, and calculating an average value.

Insulating material:

It is preferable that the said electroconductive particle is equipped with the insulating substance arrange | positioned on the surface of the said electroconductive part. In this case, when electroconductive particle is used for the connection between electrodes, the short circuit between adjacent electrodes can be prevented further. Specifically, when a plurality of conductive particles are in contact with each other, an insulating substance exists between the plurality of electrodes, and thus a short circuit between adjacent electrodes in the horizontal direction can be prevented, rather than between the upper and lower electrodes. In addition, the insulating material between the electroconductive part of electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes at the time of the connection between electrodes. When the said electroconductive particle has a some processus | protrusion in the outer surface of an electroconductive part, the insulating substance between the electroconductive part of electroconductive particle and an electrode can be removed more easily.

Since the said insulating material can be more easily excluded at the time of crimping | bonding between electrodes, it is preferable that the said insulating material is insulating particle.

As a material of the said insulating substance, the inorganic material etc. which were mentioned as the material of the above-mentioned resin particle, and the material of the base material particle mentioned above are mentioned. It is preferable that the material of the said insulating substance is the material of the above-mentioned resin particle. It is preferable that the said insulating substance is the above-mentioned resin particle or the above-mentioned organic-inorganic hybrid particle | grains, and may be a resin particle or an organic-inorganic hybrid particle | grain may be sufficient as it.

As another material of the said insulating substance, a polyolefin compound, a (meth) acrylate polymer, a (meth) acrylate copolymer, a block polymer, a thermoplastic resin, the crosslinked material of a thermoplastic resin, a thermosetting resin, a water-soluble resin, etc. are mentioned. Only 1 type may be used for the material of the said insulating substance, and 2 or more types may be used together.

As said polyolefin compound, polyethylene, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid ester copolymer, etc. are mentioned. As said (meth) acrylate polymer, polymethyl (meth) acrylate, polydodecyl (meth) acrylate, polystearyl (meth) acrylate, etc. are mentioned. Examples of the block polymers include polystyrene, styrene-acrylic acid ester copolymers, SB-type styrene-butadiene block copolymers and SBS-type styrene-butadiene block copolymers, and hydrogenated products thereof. As said thermoplastic resin, a vinyl polymer, a vinyl copolymer, etc. are mentioned. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. Examples of the crosslinking of the thermoplastic resin include introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate, and the like. As said water-soluble resin, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, methyl cellulose, etc. are mentioned. In addition, you may use a chain transfer agent for adjustment of a polymerization degree. Examples of the chain transfer agent include thiol, carbon tetrachloride, and the like.

As a method of arrange | positioning an insulating substance on the surface of the said electroconductive part, a chemical method, a physical or mechanical method, etc. are mentioned. As said chemical method, an interfacial polymerization method, suspension polymerization method, emulsion polymerization method, etc. are mentioned, for example. Examples of the physical or mechanical methods include spray drying, hybridization, electrostatic deposition, spraying, dipping and vacuum deposition. Since the insulating material is difficult to detach, it is preferable to arrange the insulating material on the surface of the conductive portion through chemical bonding.

The outer surface of the said electroconductive part and the surface of an insulating substance may respectively be coat | covered with the compound which has a reactive functional group. The outer surface of the conductive portion and the surface of the insulating material may not be directly chemically bonded, or may be chemically indirectly bonded by a compound having a reactive functional group. After introducing a carboxyl group into the outer surface of an electroconductive part, this carboxyl group may chemically couple | bond with the surface functional group of an insulating substance through polymer electrolytes, such as polyethyleneimine.

The particle diameter of the said insulating substance can be suitably selected by the particle diameter of electroconductive particle, the use of electroconductive particle, etc. The particle diameter of the said insulating substance becomes like this. Preferably it is 10 nm or more, More preferably, it is 100 nm or more, Preferably it is 4000 nm or less, More preferably, it is 2000 nm or less. When the particle diameter of an insulating substance is more than the said minimum, when electroconductive particle is disperse | distributed in binder resin, the electroconductive part in some electroconductive particle becomes difficult to contact. If the particle diameter of an insulating material is below the said upper limit, in order to exclude the insulating material between an electrode and electroconductive particle at the time of connection between electrodes, it is not necessary to make pressure high too much and also need not heat at high temperature.

The particle diameter of the said insulating substance shows a number average particle diameter. The particle diameter of the said insulating substance is calculated | required using a particle size distribution measuring apparatus etc. It is preferable that the particle diameter of an insulating substance is calculated | required by observing 50 arbitrary insulating substances with an electron microscope or an optical microscope, and calculating an average value. In electroconductive particle, when measuring the particle diameter of an insulating substance, it can measure as follows, for example.

The electroconductive particle is added to "techno-bit 4000" made from Kulzer company so that content may be 30 weight%, it disperse | distributes, and the filling resin for electroconductive particle inspection is produced. The cross section of electroconductive particle is cut out using an ion milling apparatus ("IM4000" by Hitachi High-Technologies Corporation) so that the center vicinity of the dispersed electroconductive particle in this embedding resin for inspection may be made. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification is set to 50,000 times, 50 conductive particles are randomly selected, and the insulating material of each conductive particle is observed. The particle diameter of the insulating material in each electroconductive particle is measured, they are arithmetic averaged, and it is set as the particle diameter of an insulating material.

(Conductive material)

The electrically-conductive material which concerns on this invention contains the electroconductive particle mentioned above and binder resin. It is preferable that the said electroconductive particle is disperse | distributed and used in binder resin, and it is preferable to be disperse | distributed in binder resin and to be used as an electrically-conductive material. It is preferable that the said electrically-conductive material is an anisotropic electrically-conductive material. It is preferable that the said electrically-conductive material is used for the electrical connection between electrodes. It is preferable that the said electrically-conductive material is an electrically-conductive material for circuit connection.

The binder resin is not particularly limited. As said binder resin, well-known insulating resin is used. It is preferable that the said binder resin contains a thermoplastic component (thermoplastic compound) or a curable component, and it is more preferable that a curable component is included. As said curable component, a photocurable component and a thermosetting component are mentioned. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator. It is preferable that the said thermosetting component contains a thermosetting compound and a thermosetting agent.

As said binder resin, a vinyl resin, a thermoplastic resin, curable resin, a thermoplastic block copolymer, an elastomer, etc. are mentioned, for example. Only 1 type may be used for the said binder resin, and 2 or more types may be used together.

As said vinyl resin, a vinyl acetate resin, an acrylic resin, a styrene resin, etc. are mentioned, for example. As said thermoplastic resin, a polyolefin resin, an ethylene-vinyl acetate copolymer, a polyamide resin, etc. are mentioned, for example. As said curable resin, an epoxy resin, a urethane resin, a polyimide resin, an unsaturated polyester resin, etc. are mentioned, for example. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The said curable resin may be used together with a hardening | curing agent. Examples of the thermoplastic block copolymers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated products of styrene-butadiene-styrene block copolymers, and hydrogens of styrene-isoprene-styrene block copolymers. Additives etc. are mentioned. As said elastomer, a styrene butadiene copolymer rubber, an acrylonitrile- styrene block copolymer rubber, etc. are mentioned, for example.

The conductive material is, in addition to the conductive particles and the binder resin, for example, fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents and Various additives, such as a flame retardant, may be included.

From the viewpoint of lowering the connection resistance between the electrodes more effectively and from increasing the conduction reliability between the electrodes more effectively, the viscosity (? 25) at 25 ° C of the conductive material is preferably 20 Pa · s or more, more preferably It is 30 Pa * s or more, Preferably it is 400 Pa * s or less, More preferably, it is 300 Pa * s or less. The said viscosity ((eta) 25) can be suitably adjusted with the kind and compounding quantity of a compounding component.

The said viscosity can be measured on 25 degreeC and the conditions of 5 rpm using an E-type viscometer ("TVE22L" by the Axon Sangyo Co., Ltd.) etc., for example.

The said electrically-conductive material can be used as an electrically conductive paste, an electrically conductive film, etc. When the said electrically-conductive material is a electrically conductive film, the film which does not contain electroconductive particle may be laminated | stacked on the electrically conductive film containing electroconductive particle. It is preferable that the said electrically conductive paste is an anisotropic electrically conductive paste. It is preferable that the said conductive film is an anisotropic conductive film.

In 100 weight% of said electrically-conductive materials, content of the said binder resin becomes like this. Preferably it is 10 weight% or more, More preferably, it is 30 weight% or more, More preferably, it is 50 weight% or more, Especially preferably, it is 70 weight% or more Preferably it is 99.99 weight% or less, More preferably, it is 99.9 weight% or less. When content of the said binder resin is more than the said minimum and below the said upper limit, electroconductive particle is arrange | positioned efficiently between electrodes, and the connection reliability of the connection object member connected by the electrically conductive material becomes still higher.

In 100 weight% of said electrically-conductive materials, content of the said electroconductive particle becomes like this. Preferably it is 0.01 weight% or more, More preferably, it is 0.1 weight% or more, Preferably it is 80 weight% or less, More preferably, 60 weight% or less, More preferably, it is 40 weight% or less, Especially preferably, it is 20 weight% or less, Most preferably, it is 10 weight% or less. When content of the said electroconductive particle is more than the said minimum and below the said upper limit, the conduction | electrical_connection reliability between electrodes becomes still higher.

(Connection structure)

A connection structure can be obtained by connecting a connection object member using the said electroconductive particle or the electrically-conductive material containing the said electroconductive particle and binder resin.

The said bonded structure is equipped with the connection part which connects the 1st connection object member, the 2nd connection object member, the 1st connection object member, and the 2nd connection object member, The material of the said connection part has electroconductive particle mentioned above. Or a conductive material containing the above-mentioned conductive particles and binder resin. It is preferable that the said connection part is formed of the electroconductive particle mentioned above, or is formed of the electrically-conductive material containing the electroconductive particle mentioned above and binder resin. When electroconductive particle is used, connection part itself is electroconductive particle.

It is preferable that a said 1st connection object member has a 1st electrode on the surface. It is preferable that a said 2nd connection object member has a 2nd electrode on the surface. It is preferable that the said 1st electrode and the said 2nd electrode are electrically connected by the electrically conductive part in the said electroconductive particle.

It is preferable that the said connection structure is equipped with a flexible member as said 1st connection object member or said 2nd connection object member. In this case, at least one of the said 1st connection object member and the said 2nd connection object member may be a flexible member, and both of the said 1st connection object member and the said 2nd connection object member may be a flexible member. In the state where the flexible member is curved, it is preferable that the connection structure is used. In the state in which the said connection part was curved, it is preferable that the said connection structure is used.

4 is a front sectional view schematically illustrating a bonded structure using conductive particles according to a first embodiment of the present invention.

The connection structure 51 shown in FIG. 4 includes the first connection object member 52, the second connection object member 53, the first connection object member 52, and the second connection object member 53. The connection part 54 connected is provided. The connection part 54 is formed of the electrically-conductive material containing the electroconductive particle 1. It is preferable that the said electrically-conductive material has thermosetting, and the connection part 54 is formed by thermosetting a electrically-conductive material. In addition, in FIG. 4, the electroconductive particle 1 is shown schematically for convenience of illustration. Instead of the electroconductive particle 1, you may use electroconductive particle 11, 21, etc.

The 1st connection object member 52 has some 1st electrode 52a on the surface (upper surface). The second connection object member 53 has a plurality of second electrodes 53a on its surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected by one or a plurality of conductive particles 1. Therefore, the 1st connection object member 52 and the 2nd connection object member 53 are electrically connected by the electroconductive part 3 in electroconductive particle 1.

The manufacturing method of the said bonded structure is not specifically limited. As an example of the manufacturing method of a bonded structure, after arrange | positioning the said electrically-conductive material between a 1st connection object member and a 2nd connection object member, obtaining a laminated body, the method of heating and pressurizing this laminated body, etc. are mentioned. The pressure of the thermocompression bonding is about 9.8 × 10 ⁴ to 4.9 × 10 ⁶ Pa. The heating temperature of the said thermocompression bonding is about 70-230 degreeC. The heating temperature of the said thermocompression bonding becomes like this. Preferably it is 80 degreeC or more, More preferably, it is 100 degreeC or more, Preferably it is 200 degrees C or less, More preferably, it is 150 degrees C or less. If the pressure and temperature of the said thermocompression bonding are more than the said minimum and below the said upper limit, the conduction | electrical_connection reliability between electrodes can be improved further.

Specifically as said connection object member, electronic components, such as a semiconductor chip, a capacitor | condenser, and a diode, and electronic components, such as a circuit board, such as a printed circuit board, a flexible printed circuit board, a glass epoxy substrate, and a glass substrate, etc. are mentioned. It is preferable that the said connection object member is an electronic component. It is preferable that the said electroconductive particle is used for the electrical connection of the electrode in an electronic component.

As an electrode provided in the said connection object member, metal electrodes, such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a silver electrode, a SUS electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode, are mentioned. When the said connection object member is a flexible printed circuit board, it is preferable that the said electrode is a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the said connection object member is a glass substrate, it is preferable that the said electrode is an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only of aluminum may be sufficient, and the electrode in which the aluminum layer was laminated | stacked on the surface of a metal oxide layer may be sufficient. As a material of the said metal oxide layer, indium oxide doped with a trivalent metal element, zinc oxide doped with a trivalent metal element, etc. are mentioned. Sn, Al, Ga, etc. are mentioned as said trivalent metal element.

Hereinafter, an Example and a comparative example are given and this invention is concretely demonstrated. This invention is not limited only to a following example.

(Example 1)

(1) Preparation of substrate particle

300 g of 0.13 weight% aqueous ammonia solution was put into the 500 mL reaction container provided with the stirrer and the thermometer. Next, a mixture of 1.9 g of methyltrimethoxysilane, 12.7 g of vinyltrimethoxysilane, and 0.4 g of silicon alkoxy oligomer A ("KR-517" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to an aqueous ammonia solution in the reaction vessel. Added slowly. After proceeding the hydrolysis and condensation reaction with stirring, 1.6 mL of 25% by weight aqueous ammonia solution was added, and then the particles were isolated in an aqueous ammonia solution, and the obtained particles were subjected to 2 at an oxygen partial pressure of 10 ⁻¹⁰ atm and 380 ° C. (firing temperature). It baked by time (firing time) and obtained organic-inorganic hybrid particle | grains (base material particle). The particle diameter of the obtained organic inorganic hybrid particle (base material particle A) was 3.0 micrometers.

(2) Preparation of conductive particles

After disperse | distributing 10 weight part of said substrate particles A with 100 weight part of alkaline solutions containing 5 weight% of palladium catalyst liquids using an ultrasonic disperser, the substrate particle A was taken out by filtering a solution. Subsequently, the substrate particle A was added to 100 parts by weight of a 1% by weight solution of dimethylamine borane, and the surface of the substrate particle A was activated. After sufficiently washing the substrate particle A with the surface activated, it was added to 500 weight part of distilled water, and the dispersion liquid was obtained by making it disperse | distribute. Subsequently, 1 g of alumina particle slurry (average particle diameter 150 nm) was added for 3 minutes, and added to the dispersion to obtain a suspension containing the substrate particles having a core substance attached thereto.

In addition, a nickel plating solution (pH 8.5) containing 0.35 mol / L nickel sulfate, 1.38 mol / L dimethylamine borane, and 0.5 mol / L sodium citrate was prepared.

While stirring the obtained suspension at 60 degreeC, the said nickel plating liquid was dripped gradually to suspension, and electroless nickel plating was performed. Thereafter, the suspension was filtered to remove the particles, washed with water, and dried to arrange a nickel-boron conductive layer (thickness 0.15 µm) on the surface of the substrate particle A to obtain conductive particles whose surface was a conductive layer. The surface area of the part with protrusions was 70% in 100% of the total surface area of the outer surface of the conductive portion.

(3) Preparation of Conductive Material (Anisotropic Conductive Paste)

In order to produce an electrically-conductive material (anisotropic conductive paste), the following materials were prepared.

(Material of Conductive Material (Anisotropic Conductive Paste))

Thermosetting compound A: epoxy compound ("EP-3300P" made by Nagase Chemtex company)

Thermosetting compound B: epoxy compound ("EPICLON HP-4032D" made by DIC Corporation)

Thermosetting compound C: epoxy compound ("epogose PT" made by Yokkaichi Kosei Co., polytetramethylene glycol diglycidyl ether)

Thermosetting agent: Thermal cation generator (Sun-Aid "SI-60" made by Sanshin Chemical Industries)

Filler: Silica (0.25 micrometers in average particle diameter)

A conductive material (anisotropic conductive paste) was produced as follows.

(Method for Producing Conductive Material (Anisotropic Conductive Paste))

10 weight part of thermosetting compounds A, 10 weight part of thermosetting compounds B, 15 weight part of thermosetting compounds C, 5 weight part of thermosetting agents, and 20 weight part of fillers were mix | blended, and the blend was obtained. Furthermore, after adding obtained electroconductive particle so that content in 100 weight% of formulations might be 10 weight%, the electrically-conductive material (anisotropic conductive paste) was obtained by stirring for 5 minutes at 2000 rpm using an planetary stirrer.

(4) Fabrication of bonded structure X

A polyimide substrate (flexible printed circuit board) having an Al-Ti 4% electrode pattern (Al-Ti 4% electrode thickness 1 µm) having a L / S of 20 µm / 20 µm on the upper surface was prepared. Furthermore, the semiconductor chip which L / S has a 20 micrometer / 20 micrometers gold electrode pattern (gold electrode thickness of 20 micrometers) on the lower surface was prepared.

On the upper surface of the said polyimide board | substrate, the anisotropic electrically conductive paste immediately after manufacture was coated so that it might be set to 30 micrometers in thickness, and the anisotropic electrically conductive paste layer was formed. Next, the said semiconductor chip was laminated | stacked on the upper surface of the anisotropic conductive paste layer so that electrodes may oppose. Thereafter, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer is 120 ° C., the anisotropic conductive material layer is placed on the upper surface of the semiconductor chip while giving a low pressure of 1 MPa calculated from the pressing area. It hardened | cured at 100 degreeC, and the bonded structure X was obtained.

(5) Fabrication of bonded structure Y

The bonded structure Y was produced in the same manner as the bonded structure X except that the temperature at the time of curing the anisotropic conductive material layer was changed to 150 ° C.

(6) Preparation of the connecting structure Z

The bonded structure Z was produced in the same manner as the bonded structure X except that the temperature at the time of curing the anisotropic conductive material layer was changed to 200 ° C.

(Example 2)

When producing electroconductive particle, it carried out similarly to Example 1 except having changed the alumina particle slurry into the nickel particle slurry, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 3)

When producing electroconductive particle, instead of using an alumina particle slurry for protrusion formation, it carried out similarly to Example 1 except having formed the protrusion by adjusting so that precipitation amount may partially change at the time of formation of an electroconductive part, and electroconductive particle, electroconductivity Materials and bonded structures X, Y, and Z were obtained.

(Example 4)

When producing electroconductive particle, it carried out similarly to Example 1 except having changed the alumina particle slurry into the tungsten carbide particle slurry, and obtained electroconductive particle, electroconductive material, and bonded structure X, Y, Z.

(Example 5)

When producing electroconductive particle, it carried out similarly to Example 1 except having changed the alumina particle slurry into the titanium oxide particle slurry, and obtained electroconductive particle, electroconductive material, and bonded structure X, Y, Z.

(Example 6)

When producing electroconductive particle, it carried out similarly to Example 1 except having changed the electroconductive part into the nickel-phosphorus conductive layer (phosphorus content 8weight%), and obtained electroconductive particle, electroconductive material, and bonded structure X, Y, Z.

(Example 7)

When producing electroconductive particle, the composition of the nickel plating liquid was changed and the thickness of the nickel- boron electroconductive part (thickness 0.15 micrometer) in Example 1 was changed to 0.12 micrometer. Further, a nickel plating layer (thickness of 30 nm) of high purity was formed on the outer surface of the conductive portion having changed thickness by using a nickel plating solution containing titanium (III) as a reducing agent, thereby forming a multilayer conductive portion. Except having provided the said change and the multilayer electroconductive part, it carried out similarly to Example 1, and obtained electroconductive particle, an electroconductive material, and bonded structure X, Y, Z.

(Example 8)

When producing electroconductive particle, the composition of the nickel plating liquid was changed and the thickness of the nickel- boron electroconductive part (thickness 0.15 micrometer) in Example 1 was changed to 0.12 micrometer. In addition, a nickel-tin alloy plating layer having a corrosion resistance (thickness of 30 nm) was used on the outer surface of the conductive portion whose thickness was changed by using a nickel plating solution containing titanium (III) chloride and sodium stannate trihydrate as a reducing agent and an additive. Was formed, and a multilayer conductive portion was formed. Except having provided the said change and the multilayer electroconductive part, it carried out similarly to Example 1, and obtained electroconductive particle, an electroconductive material, and bonded structure X, Y, Z.

(Example 9)

When producing electroconductive particle, the composition of the nickel plating liquid was changed and the thickness of the nickel- boron electroconductive part (thickness 0.15 micrometer) in Example 1 was changed to 0.12 micrometer. In addition, a nickel-indium alloy plating layer having a corrosion resistance was used on the outer surface of the conductive portion having this thickness changed by using a nickel plating solution containing titanium (III) chloride and indium (III) acetate as a reducing agent and an additive (thickness of 30 nm). ) Was formed, and a multilayer conductive portion was formed. Except having provided the said change and the multilayer electroconductive part, it carried out similarly to Example 1, and obtained electroconductive particle, an electroconductive material, and bonded structure X, Y, Z.

(Example 10)

When producing the substrate particles, the substrate particles B were obtained in the same manner as the substrate particles A, except that the firing temperature was changed from 380 ° C to 330 ° C. Except having used the substrate particle B instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 11)

When producing the substrate particles, the substrate particles C were obtained in the same manner as the substrate particles A, except that the firing temperature was changed from 380 ° C to 365 ° C. Except having used the substrate particle C instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 12)

When producing the substrate particles, the substrate particles D were obtained in the same manner as the substrate particles A, except that the firing temperature was changed from 380 ° C to 410 ° C. Except having used the substrate particle D instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 13)

When producing the substrate particles, the substrate particles E were obtained in the same manner as the substrate particles A, except that the firing temperature was changed from 380 ° C to 420 ° C and the oxygen partial pressure was changed from 10 ^-10 atm to 10 ^-9 atm. Except having used the substrate particle E instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 14)

The following monomer composition was put into a 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way coke, a cooling tube, and a temperature probe, and ion-exchanged water was weighed so that the solid content of the monomer composition was 5% by weight. Thereafter, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. The monomer composition includes 100 mmol of methyl methacrylate, 1 mmol of N, N, N-trimethyl-N-2-methacryloyloxyethylammonium chloride, and 2,2'-azobis (2-amidinopropane) Contains 1 mmol of acid salts. After completion | finish of reaction, it lyophilized and had an ammonium group on the surface, and obtained insulating particle of average particle diameter 220nm and CV value 10%.

Insulating particle was disperse | distributed to ion-exchange water under ultrasonic irradiation, and the 10 weight% aqueous dispersion of insulating particle was obtained.

10 g of the electroconductive particle obtained in Example 1 was disperse | distributed to 500 mL of ion-exchange water, 4 g of aqueous dispersions of insulating particle were added, and it stirred at room temperature for 6 hours. After filtering with a 3 micrometer mesh filter, it wash | cleaned further with methanol and dried, and obtained electroconductive particle with insulating particle.

When observed with the scanning electron microscope (SEM), only one coating layer by insulating particle was formed in the surface of electroconductive particle. The coverage was 40% when the coating area (namely, the projected area of the particle diameter of insulating particle) with respect to 2.5 micrometers area was computed from the center of electroconductive particle by image analysis.

Except having used the electroconductive particle with insulating particle, it carried out similarly to Example 1, and obtained the electrically-conductive material and bonded structure X, Y, Z.

(Example 15)

At the time of producing the substrate particles, the same procedure as in Example 1 was conducted except that the particle diameter of the substrate particles was changed to 5 µm, thereby obtaining the conductive particles, the conductive material, and the bonded structures X, Y, and Z.

(Example 16)

When producing electroconductive particle, the composition of the nickel plating liquid was changed, the electroconductive part was changed into the nickel-phosphorus conductive layer (phosphorus content 8 weight%, thickness 0.13 micrometer), and the gold plating layer (thickness 0.02 on the surface of a nickel-phosphorus conductive layer). Except having formed (micrometer), it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 17)

When producing electroconductive particle, it carried out similarly to Example 1 except having provided the gold plating layer (thickness 0.02 micrometer) on the surface of a nickel- boron conductive layer, and electroconductive particle, an electroconductive material, and connection structure X, Y, Z Got it.

(Example 18)

When producing electroconductive particle, it carried out similarly to Example 7 except having formed the gold plating layer (thickness 0.02 micrometer) on the surface of the high purity nickel plating layer, and obtained electroconductive particle, electroconductive material, and bonded structure X, Y, Z. .

(Example 19)

When producing electroconductive particle, the composition of the nickel plating liquid was changed, the electroconductive part was changed into the nickel-phosphorus conductive layer (phosphorus content 8weight%, thickness 0.13micrometer), and the palladium plating layer (thickness 0.02 on the surface of a nickel-phosphorus conductive layer) Except having formed (micrometer), it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 20)

When producing electroconductive particle, it carried out similarly to Example 1 except having provided the palladium plating layer (thickness 0.02 micrometer) on the surface of a nickel- boron conductive layer, and electroconductive particle, electroconductive material, and bonded structure X, Y, Z Got it.

(Example 21)

When producing electroconductive particle, it carried out similarly to Example 7 except having provided the palladium plating layer (thickness 0.02 micrometer) on the surface of the high purity nickel plating layer, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z. .

(Example 22)

When producing the substrate particles, the particle diameter of the substrate particles was changed from 3.0 µm to 1.0 µm, and the composition of the nickel plating solution was changed when producing the conductive particles, and the nickel-boron conductive portion in Example 1 (thickness 0.15 µm) Except having changed the thickness of into 0.075 micrometer, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 23)

When producing the substrate particles, the particle diameter of the substrate particles was changed from 3.0 µm to 2.0 µm, and the composition of the nickel plating solution was changed when producing the conductive particles, and the nickel-boron conductive portion in Example 1 (thickness 0.15 µm) Except having changed the thickness of into 0.075 micrometer, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Example 24)

As the seed particles, polystyrene particles having an average particle diameter of 0.80 mu m were prepared. 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution were mixed, dispersed by ultrasonic wave, added to a pressure-resistant hermetic polymerizer, and stirred uniformly.

Subsequently, 2.0 parts by weight of t-butylperoxybenzoate ("perbutyl Z" manufactured by Nichi Oil) and 2.0 parts by weight of benzoyl peroxide ("Niper BW" manufactured by Nichi Oil) were dissolved in 120 parts by weight of divinylbenzene as a monomer. And the solution was obtained. 5.0 weight part of lauryl sulfate triethanolamine, 60 weight part of ethanol, and 1000 weight part of ion-exchange water were added to the obtained solution, and the emulsion was obtained.

The obtained emulsion liquid was further added to the pressure-resistant closed polymerizer to which the polystyrene particles as the seed particles were added, and stirred for 4 hours to absorb the monomers into the seed particles, thereby obtaining a suspension containing the seed particles in which the monomer was swollen.

490 weight part of 5 weight% polyvinyl alcohol aqueous solution was added to the obtained suspension, heating was started, and it was made to react at 140 degreeC for 6 hours, and the base material particle F of 3.08 micrometers of particle diameters was obtained.

Except having used the substrate particle F instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Comparative Example 1)

When producing the substrate particles, the substrate particles G were obtained in the same manner as the substrate particles A, except that the firing temperature was changed from 380 ° C to 120 ° C. Except having used the substrate particle G instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Comparative Example 2)

When producing the substrate particles, the substrate particles H were obtained in the same manner as the substrate particles A, except that 1.9 g of methyltrimethoxysilane was changed to 8.8 g and 12.7 g of vinyltrimethoxysilane was changed to 5.8 g. . Except having used the substrate particle H instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(Comparative Example 3)

As the seed particles, polystyrene particles having an average particle diameter of 0.8 μm were prepared. 2.5 g of the polystyrene particles, 500 g of ion-exchanged water, and 100 g of a 5 wt% polyvinyl alcohol aqueous solution were mixed, dispersed by ultrasonic waves, added to a separable flask, and stirred uniformly.

Further, 6.3 g of benzoyl peroxide (Nipper BW), 30 g of lauryl triethanolamine, and 243 g of N, N-dimethylformamide were added to 1100 g of ion-exchanged water to prepare an emulsion.

In addition, 78 g of 1,4-butanediol diacrylate was prepared as a monomer.

The monomer and the emulsifier were further added to the separable flask to which the polystyrene particles as the seed particles were added, stirred for 12 hours, and the monomer was absorbed into the seed particles. Subsequently, 500 g of a 5% by weight polyvinyl alcohol aqueous solution was added, and the substrate particles I were obtained by reacting for 9 hours.

Except having used the substrate particle I instead of the substrate particle A, it carried out similarly to Example 1, and obtained electroconductive particle, an electrically-conductive material, and bonded structure X, Y, Z.

(evaluation)

(1) 10% K value

10% K value at 25 ° C, 10% K value at 100 ° C, 10% K value at 150 ° C, and 200 ° C of the conductive particles obtained using an ultra-fine indentation hardness tester Fisherscope HM2000 manufactured by H.FISCHER 10% K value of was measured by the method mentioned above. From the obtained measurement result, ratio with respect to 10% K value in 25 degreeC of 10% K value in 100 degreeC, ratio with respect to 10% K value in 25 degreeC of 10% K value in 150 degreeC, and 200 degreeC The ratio with respect to 10% K value in 25 degreeC of the 10% K value in was computed. In addition, the heating of 100 degreeC, 150 degreeC, and 200 degreeC heated the measurement stage with a heater so that the surface of a measurement stage might be 100 degreeC, 150 degreeC, and 200 degreeC.

(2) 20% K value

The 20% K value at 25 degreeC, the 20% K value at 100 degreeC, the 20% K value at 150 degreeC, and the 20% K value at 200 degreeC of the obtained electroconductive particle were measured by the method mentioned above. From the obtained measurement result, ratio with respect to 20% K value in 25 degreeC of 20% K value in 100 degreeC, ratio with respect to 20% K value in 25 degreeC of 20% K value in 150 degreeC, and 200 degreeC The ratio with respect to 20% K value in 25 degreeC of the 20% K value in was computed.

(3) 30% K value

30% K value at 25 degreeC, 30% K value at 100 degreeC, 30% K value at 150 degreeC, and 30% K value at 200 degreeC of the obtained electroconductive particle were measured by the method mentioned above. From the obtained measurement result, ratio with respect to 30% K value at 25 degreeC of 30% K value at 100 degreeC, ratio with respect to 30% K value at 25 degreeC of 30% K value at 150 degreeC, and 200 degreeC The ratio with respect to 30% K value in 25 degreeC of 30% K value in was computed.

(4) 40% K value

40% K value at 25 degreeC, 40% K value at 100 degreeC, 40% K value at 150 degreeC, and 40% K value at 200 degreeC of the obtained electroconductive particle were measured by the method mentioned above. From the obtained measurement result, ratio with respect to 40% K value at 25 degreeC of 40% K value at 100 degreeC, ratio with respect to 40% K value at 25 degreeC of 40% K value at 150 degreeC, and 200 degreeC The ratio with respect to 40% K value in 25 degreeC of 40% K value in was computed.

(5) compression recovery rate

The compression recovery rate at 25 ° C., the compression recovery rate at 100 ° C., the compression recovery rate at 150 ° C., and the compression recovery rate at 200 ° C. of the obtained conductive particles were measured by the method described above.

(6) particle diameter

The particle diameter of the obtained electroconductive particle was measured using the "Laser diffraction type particle size distribution measuring apparatus" by Horiba Corporation. In addition, the particle diameter of electroconductive particle was computed by averaging 20 measurement result.

(7) Continuity Reliability (Initial)

The connection resistance A between the upper and lower electrodes of the obtained bonded structures X, Y, and Z was measured by the four-terminal method, respectively. Moreover, the connection resistance A can be calculated | required by measuring the voltage at the time of making a constant current flow from the relationship of voltage = current x resistance. The conduction reliability (initial stage) was determined from the connection resistance A based on the following criteria.

[Judgment criterion of conduction reliability (initial)]

○○○: Connection resistance A is 2.0Ω or less

○ ○: Connection resistance A exceeds 2.0 Ω and is 3.0 Ω or less

○: Connection resistance A exceeds 3.0 Ω and 5.0 Ω or less

Δ: Connection resistance A exceeds 5.0 Ω and 10 Ω or less

X: Connection resistance A exceeds 10 ohms

(8) Conduction reliability after high temperature, high humidity

The bonded structure X, Y, Z after evaluation of said (7) connection resistance was left to stand on 85 degreeC and the conditions of 85% of humidity for 500 hours. In the bonded structures X, Y, and Z after leaving for 500 hours, the connection resistance B between the upper and lower electrodes was measured by the four-terminal method, respectively. The conduction reliability after high temperature, high humidity standing from connection resistance A and B was determined on the following reference | standard.

[Judgment criterion of conduction reliability after high temperature, high humidity]

○○○: Connection resistance B is less than 1.25 times connection resistance A

(Circle): Connection resistance B is 1.25 times or more and less than 1.5 times of connection resistance A

○: connection resistance B is 1.5 times or more and less than 2 times of connection resistance A

(Triangle | delta): Connection resistance B is 2 times or more and less than 5 times of connection resistance A

X: Connection resistance B is 5 times or more of connection resistance A

The results are shown in Tables 1 to 6 below. In the table, the unit of K value is "N / mm <2>", and the unit of a compression recovery rate is "%".

1: conductive particles
2: substrate particle
3: challenge
11: conductive particles
11a: turning
12: Challenge
12a: turning
13: core material
14: insulating material
21: conductive particles
21a: turning
22: challenge
22a: turning
22A: first conductive portion
22Aa: Turning
22B: Second Conductive Part
22Ba: turning
51: connection structure
52: first connection target member
52a: first electrode
53: second connection object member
53a: second electrode
54: connection

Claims (15)

The ratio of the 20% K value at 100 ° C to the 20% K value at 25 ° C is 0.85 or less, the compression recovery rate at 25 ° C is 50% or more and 80% or less, and the compression recovery rate at 100 ° C is 40% or more. 1st structure which is 70% or less, or
The ratio of the 20% K value at 150 ° C to the 20% K value at 25 ° C is 0.75 or less, the compression recovery rate at 25 ° C is 50% or more and 80% or less, and the compression recovery rate at 150 ° C is 25% or more. Or having a second configuration that is 55% or less, or
The ratio of 20% K value at 200 ° C to 20% K value at 25 ° C is 0.65 or less, the compression recovery rate at 25 ° C is 50% or more and 80% or less, and the compression recovery rate at 200 ° C is 20% or more. Electroconductive particle provided with the 3rd structure which is 50% or less. Electroconductive particle of Claim 1 provided with the said 1st structure. Electroconductive particle of Claim 1 provided with the said 2nd structure. Electroconductive particle of Claim 1 provided with the said 3rd structure. Electroconductive particle of Claim 2 whose 20% K value in said 100 degreeC is 5000 N / mm <2> or more and 16000 N / mm <2> or less. Electroconductive particle of Claim 3 whose 20% K value in said 150 degreeC is 4500 N / mm <2> or more and 15000 N / mm <2> or less. Electroconductive particle of Claim 4 whose 20% K value in said 200 degreeC is 4000 N / mm <2> or more and 14000 N / mm <2> or less. Electroconductive particle of any one of Claims 1-7 whose 20% K value in said 25 degreeC is 8000 N / mm <2> or more and 20000 N / mm <2> or less. Electroconductive particle of any one of Claims 1-8 whose particle diameter exceeds 1 micrometer. Electroconductive particle of any one of Claims 1-9 provided with a substrate particle and the electroconductive part arrange | positioned on the surface of the said substrate particle. Electroconductive particle of Claim 10 whose said substrate particle is an organic-inorganic hybrid particle. Electroconductive particle of any one of Claims 1-11 used for the electrically conductive connection use of the electrode of the flexible member of the curved state. The electrically-conductive material containing the electroconductive particle of any one of Claims 1-12, and binder resin. The first connection object member which has a 1st electrode on the surface,
2nd connection object member which has a 2nd electrode on the surface,
It is provided with the connection part which connects the said 1st connection object member and the said 2nd connection object member,
The material of the said connection part is the electroconductive particle of any one of Claims 1-12, or the electrically-conductive material containing the said electroconductive particle and binder resin,
The said 1st electrode and said 2nd electrode are electrically connected by the electrically conductive part in the said electroconductive particle. The said 1st connection object member or the said 2nd connection object member, A flexible member is provided,
A bonded structure, wherein the bonded structure is used in a state where the flexible member is curved.

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