KR20210154865A - Metal-containing particle, connecting material, connected structure, and method for producing connected structure - Google Patents

Abstract

Provided is a metal-containing particle in which the tip of the projection of the metal part of the metal-containing particle can be melted at a relatively low temperature and solidified after melting, so that it can be joined to other particles or other members, thereby improving connection reliability. The metal containing particle which concerns on this invention is equipped with a substrate particle and the metal part arrange|positioned on the surface of the said substrate particle, The said metal part has a some protrusion on the outer surface, The front-end|tip of the said protrusion of the said metal part is 400 degrees C or less can be melted in

Description

Metal-containing particles, connection material, bonded structure, and manufacturing method of bonded structure TECHNICAL FIELD

This invention is equipped with a substrate particle and the metal part arrange|positioned on the surface of this substrate particle, The said metal part relates to the metal containing particle|grain which has a processus|protrusion on the outer surface. Moreover, this invention relates to the manufacturing method of the connection material, bonded structure, and bonded structure using the said metal containing particle|grains.

In an electronic component etc., in order to form the connection part which connects two connection object members, the connection material containing a metal particle may be used.

It is known that when the particle size of the metal particles decreases to a size of 100 nm or less and the number of constituent atoms decreases, the surface area ratio to the volume of the particles increases rapidly, and the melting point or sintering temperature decreases significantly compared to the bulk state. Using this low-temperature sintering function, using metal particles having a particle diameter of 100 nm or less as a connection material, there is known a method of performing connection by sintering metal particles by heating. In this connection method, since the metal particle after connection changes to a bulk metal and connection by a metal bond is obtained at a connection interface, heat resistance, connection reliability, and heat dissipation property become very high.

The connection material for performing such a connection is disclosed by the following patent document 1, for example.

The connecting material described in Patent Document 1 contains nano-sized composite silver particles, nano-sized silver particles, and resin. The composite silver particles are particles in which an organic coating layer is formed around a silver nucleus that is an aggregate of silver atoms. The organic coating layer is formed of an alcohol molecular residue having 10 or 12 carbon atoms, an alcohol molecular derivative (herein, the alcohol molecular derivative is limited to a carboxylic acid and/or an aldehyde), and/or one or more alcohol components of an alcohol molecule.

Moreover, the following patent document 2 discloses the connection material containing nano-sized metal containing particle|grains and electroconductive particle.

Japanese Patent No. 5256281 Japanese Patent Laid-Open No. 2013-55046

Metal particles, such as nano-sized silver particles, are melt-bonded by heat treatment at the time of connection to form a bulk. When bulk is formed, since melting|fusing point becomes high, there exists a problem that a heating temperature becomes high. In addition, in the formed bulk, gaps are generated between the nano-sized particles. As a result, the connection reliability becomes low.

Moreover, in patent document 1, since the said composite silver particle has an alcohol component on the surface, it originates in this alcohol component, and a void is easy to generate|occur|produce in a connection part. As a result, connection reliability is lowered.

It is an object of the present invention to provide metal-containing particles that can be bonded to other particles or other members by melting the tip of the projection of the metal part of the metal-containing particle at a relatively low temperature and solidifying it after melting, thereby improving the connection reliability. will be. Moreover, this invention also aims at providing the manufacturing method of the connection material, bonded structure, and bonded structure using the said metal containing particle|grains.

According to the broad situation of this invention, a substrate particle and the metal part arrange|positioned on the surface of the said substrate particle are provided, the said metal part has a some processus|protrusion on the outer surface, The front-end|tip of the said processus|protrusion of the said metal part is 400 degrees C or less. Meltable, metal-containing particles are provided.

In a specific aspect of the metal-containing particles according to the present invention, the metal part has a plurality of convex parts on the outer surface, and the metal part has the projections on the outer surface of the convex parts.

In a specific situation of the metal-containing particles according to the present invention, the ratio of the average height of the convex portions to the average height of the projections is 5 or more and 1000 or less.

On the specific situation with the metal-containing particle|grains which concern on this invention, the average diameter of the base part of the said convex part is 3 nm or more and 5000 nm or less.

In a specific situation of the metal-containing particles according to the present invention, the surface area of the convex portion is 10% or more among 100% of the total surface area of the outer surface of the metal portion.

In a specific aspect of the metal-containing particle according to the present invention, the shape of the convex portion is a needle-like shape or a partial shape of a sphere.

In a specific aspect of the metal-containing particles according to the present invention, the average of the vertex angles of the projections is 10° or more and 60° or less.

In a specific aspect of the metal-containing particles according to the present invention, the average height of the projections is 3 nm or more and 5000 nm or less.

In a specific aspect of the metal-containing particles according to the present invention, the average diameter of the base of the projections is 3 nm or more and 1000 nm or less.

In a specific aspect of the metal-containing particles according to the present invention, the ratio of the average height of the projections to the average diameter of the base of the projections is 0.5 or more and 10 or less.

In a specific aspect of the metal-containing particle according to the present invention, the shape of the projection is a needle-like shape or a partial shape of a sphere.

In certain specific aspects of the metal-containing particles according to the present invention, the material of the protrusions comprises silver, copper, gold, palladium, tin, indium or zinc.

In certain specific aspects of the metal-containing particles according to the present invention, the material of the metal part is not solder.

In certain specific aspects of the metal-containing particles according to the present invention, the material of the metal part is silver, copper, gold, palladium, tin, indium, zinc, nickel, cobalt, iron, tungsten, molybdenum, ruthenium, platinum, rhodium, iridium, phosphorus or boron.

In a specific aspect of the metal-containing particle according to the present invention, the tip of the projection of the metal part is preferably meltable at 350°C or lower, more preferably meltable at 300°C or lower, still more preferably 250°C or lower. It can be melted at or below, particularly preferably at 200°C or lower.

In a particular aspect of the metal-containing particles according to the present invention, the compression modulus is 100N / mm ² or more 25000N / mm ² or less at the time when compressed 10%.

On the specific situation with the metal containing particle which concerns on this invention, the said substrate particle is a silicon particle.

According to a broad aspect of the present invention, there is provided a connecting material comprising the above-described metal-containing particles and a resin.

According to the broad aspect of this invention, a 1st connection object member, a 2nd connection object member, and the connection part which connects the said 1st connection object member and the said 2nd connection object member are provided, The material of the said connection part is the above-mentioned A bonded structure is provided, which is one metal-containing particle or a connection material containing the metal-containing particle and a resin.

According to a broad aspect of the present invention, there is provided a step of disposing the above-described metal-containing particles or disposing a connection material comprising the metal-containing particles and a resin between the first connection object member and the second connection object member, the method comprising: The metal-containing particles are heated to melt the tip of the protrusion of the metal part and solidify after melting, so that the first connection object member and the second connection object member are connected by the metal-containing particles or the connection material, A method for manufacturing a bonded structure is provided, comprising the step of forming a connection portion with an attached portion.

The metal-containing particle which concerns on this invention is equipped with a substrate particle and the metal part arrange|positioned on the surface of this substrate particle, the said metal part has a some processus|protrusion on the outer surface, The front-end|tip of the said processus|protrusion of the said metal part is 400 degrees C or less Since it can be melted in a metal-containing particle, the tip of the protrusion of the metal part of the metal-containing particle is melted at a relatively low temperature and solidified after melting, so that it can be joined to other particles or other members, so that connection reliability can be improved.

1 is a cross-sectional view schematically showing metal-containing particles according to a first embodiment of the present invention.
2 is a cross-sectional view schematically showing metal-containing particles according to a second embodiment of the present invention.
3 is a cross-sectional view schematically showing metal-containing particles according to a third embodiment of the present invention.
4 is a cross-sectional view schematically showing metal-containing particles according to a fourth embodiment of the present invention.
5 is a cross-sectional view schematically showing metal-containing particles according to a fifth embodiment of the present invention.
6 is a cross-sectional view schematically showing metal-containing particles according to a sixth embodiment of the present invention.
7 is a cross-sectional view schematically showing metal-containing particles according to a seventh embodiment of the present invention.
8 is a cross-sectional view schematically showing metal-containing particles according to an eighth embodiment of the present invention.
9 is a cross-sectional view schematically showing a bonded structure using metal-containing particles according to the first embodiment of the present invention.
It is sectional drawing which shows typically the modified example of the bonded structure using the metal-containing particle|grains which concern on 1st Embodiment of this invention.
11 : is a figure which shows the image of the manufactured metal containing particle|grains.
12 : is a figure which shows the image of the manufactured metal containing particle|grains.
13 : is a figure which shows the image of the manufactured metal containing particle|grains.
14 : is a figure which shows the image of the manufactured metal containing particle|grains.
Fig. 15 is a view showing an image of particles obtained by melting and then solidifying the tip of the projection of the metal part of the produced metal-containing particles.
Fig. 16 is a view showing an image of particles obtained by melting and then solidifying the tip of the projection of the metal part of the produced metal-containing particles.
Fig. 17 is a view showing an image of particles obtained by melting and then solidifying the tip of the projection of the metal part of the produced metal-containing particles.
Fig. 18 is a view showing an image of particles obtained by melting and then solidifying the tip of the projection of the metal part of the produced metal-containing particles.
19A and 19B are a plan view and a cross-sectional view showing an example of a member for conduction inspection.
20A to 20C are diagrams schematically showing a state in which the electrical characteristics of an electronic circuit device are inspected by a member for conduction inspection.

EMBODIMENT OF THE INVENTION Hereinafter, the detail of this invention is demonstrated.

(Metal-containing particles)

The metal containing particle which concerns on this invention is equipped with a substrate particle and a metal part. The said metal part is arrange|positioned on the surface of the said substrate particle. In the metal-containing particle according to the present invention, the metal portion has a plurality of projections on the outer surface. In the metal-containing particle according to the present invention, the tip of the projection of the metal part can be melted at 400° C. or less.

In this invention, since the said structure is provided, the front-end|tip of the projection of a metal part can be melt|melted at comparatively low temperature. For this reason, the tip of the projection of the metal part in the metal-containing particle can be melted at a relatively low temperature and solidified after melting, so that it can be joined to other particles or other members. In addition, a plurality of metal-containing particles can be melt-bonded. In addition, the metal-containing particles can be melt-bonded to the member to be connected. In addition, the metal-containing particles may be melt-bonded to the electrode.

It is known that when the particle size of the metal particles decreases to a size of 100 nm or less and the number of constituent atoms decreases, the surface area ratio to the volume of the particles increases rapidly, and the melting point or sintering temperature decreases significantly compared to the bulk state. The present inventors have discovered that, by reducing the diameter of the tip of the protrusion of the metal part, the melting temperature of the tip of the protrusion of the metal part can be lowered, similarly to the case where nano-sized metal particles are used.

In order to lower the melting temperature of the tip of the projection of the metal portion, the shape of the projection portion may be a needle-like shape tapering toward the end. In order to lower the melting temperature of the tip of the projection of the metal portion, a plurality of small projections may be formed on the outer surface of the metal portion. In order to lower the melting temperature of the tip of the protrusion of the metal part, in the metal-containing particle according to the present invention, the metal part has a plurality of convex parts (first protrusions) on the outer surface, and the metal part is on the outer surface of the convex part. It is preferable to have the said projection (second projection). It is preferable that the said convex part is larger than the said protrusion. Apart from the projections, the presence of the convex portion larger than the projections further increases the connection reliability. The projections and the projections may be integrated, or the projections may be attached to the projections. The said processus|protrusion may be comprised from particle|grains. In the present specification, to distinguish the projection from the projection, the projection portion in which the projection is formed on the outer surface is referred to as a convex portion. The tip of the convex portion does not need to be meltable at 400°C or lower.

In this way, the melting temperature can be lowered by reducing the diameter of the tip of the protrusion. In addition, the material of the metal part can be selected in order to lower the melting temperature. In order to set the melting temperature of the tip of the projection of the metal portion to 400° C. or less, it is preferable to select the shape of the projection and the material of the metal portion.

The melting temperature of the tip of the projection of the metal part is evaluated as follows.

The melting temperature of the tip of the projection of the metal part can be measured using a differential scanning calorimeter (“DSC-6300” manufactured by Yamato Chemical Co., Ltd.). The above measurement is performed using 15 g of metal-containing particles under measurement conditions of a temperature increase range of 30°C to 500°C, a temperature increase rate of 5°C/min., and a nitrogen purge amount of 5 ml/min.

Then, it is confirmed that the tip of the projection of the metal part is melted at the melting temperature obtained in the above measurement. 1 g of metal-containing particles are placed in a container and placed in an electric furnace. In an electric furnace, the same temperature as the melting temperature obtained by the above measurement was set, and heated in a nitrogen atmosphere for 10 minutes. Thereafter, the heated metal-containing particles are taken out from the electric furnace, and the molten state (or the solidified state after melting) of the tip of the projection is confirmed using a scanning electron microscope.

From the viewpoint of effectively lowering the melting temperature of the tip of the protrusion and effectively increasing the connection reliability, the shape of the protrusion is preferably a needle-like shape that tapers toward the end. In this metal-containing particle, the shape of the projection on the outer surface of the metal part is different from the conventional shape, and a new effect is exhibited by the shape of the projection being a needle-like shape that tapers toward the end.

Since the metal-containing particle according to the present invention can melt-bond the tip of the projection of the metal part at a relatively low temperature, it can be used for connection of two members to be connected. By fusion bonding between the two connection target members at the tip of the projection of the metal part in the metal-containing particle, a connection portion exhibiting a strong connection can be formed, and connection reliability can be improved.

Further, the metal-containing particles according to the present invention may be used for conductive connection. Further, the metal-containing particles according to the present invention can also be used as a gap control material (spacer).

The average (a) of the vertex angles of the plurality of projections is preferably 10° or more, more preferably 20° or more, preferably 60° or less, and more preferably 45° or less. When the average (a) of the vertex angles is equal to or greater than the lower limit, the projections are unlikely to be excessively bent. When the average (a) of the vertex angles is equal to or less than the upper limit, the melting temperature is further lowered. Moreover, the bent protrusion may raise the connection resistance between electrodes at the time of a conductive connection.

The average (a) of the vertex angles of the projections is obtained by averaging the vertex angles of the projections included in one metal-containing particle.

The average height (b) of the plurality of projections is preferably 3 nm or more, more preferably 5 nm or more, still more preferably 50 nm or more, preferably 5000 nm or less, more preferably 1000 nm or less, still more preferably 800 nm or less. is below. When the average height (b) of the projections is equal to or greater than the lower limit, the melting temperature is further lowered. When the average height (b) of the projections is equal to or less than the upper limit, the projections are unlikely to be excessively bent.

The average height (b) of the projections is an average of the heights of the projections included in one metal-containing particle. When the metal part does not have the convex part and has the protrusion, the height of the protrusion is assumed to be absent on the line connecting the center of the metal-containing particle and the tip of the protrusion (dashed line L1 shown in Fig. 1). The distance from the imaginary line (dashed line L2 shown in FIG. 1) of the metal part in this case (on the outer surface of the spherical metal-containing particle in the case of assuming that there is no processus|protrusion) to the front-end|tip of a processus|protrusion is shown. That is, in FIG. 1, the distance from the intersection of the broken line L1 and the broken line L2 to the front-end|tip of a processus|protrusion is shown. Moreover, when the said metal part has the said convex part and has the said protrusion, that is, when the said metal part has the said protrusion on the said convex part, the height of the said protrusion is a metal part (convexity) at the time of assuming no protrusion. The distance from the imaginary line of part) to the tip of the protrusion is indicated. The protrusion may be an aggregate of a plurality of granular objects. For example, the protrusion may be formed by connecting a plurality of particles constituting the protrusion. In this case, the height of the projection is the height of the projection when the aggregate of the plurality of granular objects or the connected particles are viewed as a whole. Also in FIG. 3, the height of protrusion 1Ba, 3Ba shows the distance from the imaginary line of the metal part at the time of assuming that there is no protrusion to the front-end|tip of a processus|protrusion.

The average diameter (c) of the bases of the plurality of projections is preferably 3 nm or more, more preferably 5 nm or more, still more preferably 50 nm or more, preferably 1000 nm or less, and more preferably 800 nm or less. When the said average diameter c is more than the said minimum, a processus|protrusion becomes difficult to bend excessively. Connection reliability becomes still higher that the said average diameter c is below the said upper limit.

The average diameter c of the base of the protrusions is an average of the diameters of the bases of the protrusions contained in one metal-containing particle. The diameter of the base is the respective maximum diameter of the base in the protrusion. When the metal part has the convex part and has the protrusion, that is, when the metal part has the protrusion on the convex part, on the line connecting the center of the metal-containing particle and the tip of the protrusion, the protrusion is The end of the virtual line part of the metal part in the case of assuming that there is no is the base of the said projection, and the distance between the ends of the said virtual line part (the distance which connected the end by a straight line) is the diameter of the base.

The ratio of the average height (b) of the plurality of projections to the average diameter (c) of the bases of the plurality of projections (average height (b)/average diameter (c)) is preferably 0.5 or more, more preferably is 1.5 or more, preferably 10 or less, and more preferably 5 or less. Connection reliability becomes still higher that the said ratio (average height (b)/average diameter (c)) is more than the said minimum. When the said ratio (average height (b)/average diameter (c)) is below the said upper limit, a processus|protrusion becomes difficult to bend excessively.

Preferably, the ratio (average diameter d/average diameter c) of the average diameter d at the central position of the heights of the plurality of projections to the average diameter c of the bases of the plurality of projections is 1/5 or more, more preferably 1/4 or more, still more preferably 1/3 or more, preferably 4/5 or less, more preferably 3/4 or less, still more preferably 2/3 or less. . When the said ratio (average diameter (d)/average diameter (c)) is more than the said lower limit, a processus|protrusion becomes difficult to bend excessively. When the ratio (average diameter (d)/average diameter (c)) is equal to or less than the upper limit, the connection reliability is further improved.

The average diameter d at the central position of the heights of the projections is an average of the diameters at the central positions of the heights of the projections contained in one metal-containing particle. The diameter at the central position of the height of the projection is the respective maximum diameter of the central position of the height of the projection.

From the viewpoint of suppressing excessive bending of the projections, further enhancing the fusion bonding property by the projections, and effectively improving the connection reliability, the shape of the plurality of projections is preferably a needle-like shape or a partial shape of a spherical body. It is preferable that the shape of an acicular shape is a pyramid shape, conical shape, or rotation parabolic shape, It is more preferable that it is conical shape or rotation parabolic shape, It is more preferable that it is conical shape. The shape of the said processus|protrusion may be prismatic, conical shape may be sufficient as it, and rotational parabolic shape may be sufficient as it. In the present invention, the rotational parabolic image is also included in the bed tapering toward the end. In a rotational parabolic protrusion, it tapers toward the end from the base to the front-end|tip.

The number of protrusions on the outer surface of the metal part per one metal-containing particle is preferably 3 or more, more preferably 5 or more. The upper limit of the number of the projections is not particularly limited. The upper limit of the number of projections can be appropriately selected in consideration of the particle diameter of the metal-containing particles and the like. In addition, the projections included in the metal-containing particles may not be needle-like tapering toward the tip, and all projections included in the metal-containing particles do not need to be needle-like tapering toward the tip.

The ratio of the number of acicular protrusions tapering toward the tip to the number of protrusions contained per one metal-containing particle is preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, Especially preferably, it is 70 % or more, Especially preferably, it is 80 % or more. The greater the ratio of the number of needle-like projections, the more effectively the effect of the needle-like projections is obtained.

The ratio (x) of the surface area of the protruding portion out of 100% of the total surface area of the outer surface of the metal part is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, and preferably It is 90 % or less, More preferably, it is 80 % or less, More preferably, it is 70 % or less. The greater the ratio of the surface area of the protrusion, the more effectively the effect of the protrusion is obtained.

From the viewpoint of effectively improving the connection reliability, the ratio of the surface area of the needle-like protrusion to 100% of the total surface area of the outer surface of the metal part is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more. % or more, preferably 90% or less, more preferably 80% or less, still more preferably 70% or less. The more the ratio of the surface area of the needle-like protrusion is, the more effectively the effect of the protrusion is obtained.

The average (A) of the vertex angles of the plurality of convex portions is preferably 10° or more, more preferably 20° or more, preferably 60° or less, and more preferably 45° or less. When the average (A) of the vertex angles is equal to or greater than the lower limit, the convex portions are unlikely to be excessively bent. When the average (A) of the vertex angles is equal to or less than the upper limit, the melting temperature is further lowered. Moreover, the bent convex part may raise the connection resistance between electrodes at the time of a conductive connection.

The average (A) of the vertex angles of the convex portions is obtained by averaging the vertex angles of the convex portions included in one metal-containing particle.

The average height (B) of the plurality of convex portions is preferably 5 nm or more, more preferably 50 nm or more, preferably 5000 nm or less, more preferably 1000 nm or less, still more preferably 800 nm or less. When the average height B of the said convex part is more than the said minimum, a melting temperature becomes still lower. When the average height B of the said convex part is below the said upper limit, it becomes difficult for a convex part to bend excessively.

The average height B of the convex portions is an average of the heights of the convex portions included in one metal-containing particle. The height of the convex part is on a line (dashed line L1 shown in Fig. 8) connecting the center of the metal-containing particle and the tip of the convex part on an imaginary line (dashed line L2 shown in Fig. 8) of the metal part when it is assumed that there is no convex part ( The distance from the outer surface) of the spherical metal-containing particle|grains at the time of assuming that there is no convex part to the front-end|tip of a convex part is shown. That is, in FIG. 8, the distance from the intersection of the broken line L1 and the broken line L2 to the front-end|tip of a convex part is shown.

The average diameter (C) of the bases of the plurality of convex portions is preferably 3 nm or more, more preferably 5 nm or more, still more preferably 50 nm or more, preferably 5000 nm or less, more preferably 1000 nm or less, still more preferably is less than 800 nm. When the said average diameter C is more than the said minimum, a convex part becomes difficult to bend excessively. Connection reliability becomes still higher that the said average diameter C is below the said upper limit.

The average diameter (C) of the base of the convex part is an average of the diameter of the base of the convex part contained in one metal-containing particle. The diameter of the base is the respective maximum diameter of the base in the convex portion. On the line connecting the center of the metal-containing particle and the tip of the convex part (dashed line L1 shown in Fig. 8), the edge of the imaginary line portion (dashed line L2 shown in Fig. 8) of the metal part when it is assumed that there is no convex part is the convex It is a negative base, and the distance between the ends of the said imaginary line part (a distance connecting the ends by a straight line) is the diameter of the base.

Preferably, the ratio (average diameter (D)/average diameter (C)) of the average diameter (D) at the central position of the heights of the plurality of convex portions to the average diameter (C) of the bases of the plurality of convex portions 1/5 or more, more preferably 1/4 or more, still more preferably 1/3 or more, preferably 4/5 or less, more preferably 3/4 or less, still more preferably 2/3 or less. . When the said ratio (average diameter (D)/average diameter (C)) is more than the said lower limit, a convex part becomes difficult to bend excessively. Connection reliability becomes still higher that the said ratio (average diameter (D)/average diameter (C)) is below the said upper limit.

The average diameter D at the central position of the height of the convex portion is an average of the diameters at the central position of the height of the convex portion contained in one metal-containing particle. The diameter at the central position of the height of the convex portion is each maximum diameter at the central position of the height of the convex portion.

From a viewpoint of suppressing excessive bending of a convex part, further improving the melt bondability by a convex part, and improving connection reliability effectively, it is preferable that the shape of several said convex part is a needle shape or a part shape of a spherical shape. It is preferable that the shape of an acicular shape is a pyramid shape, conical shape, or rotation parabolic shape, It is more preferable that it is conical shape or rotation parabolic shape, It is more preferable that it is conical shape. The shape of the said convex part may be prismatic, conical shape may be sufficient as it, and rotational parabolic shape may be sufficient as it. In the present invention, the rotational parabolic image is also included in the bed tapering toward the end. In the convex portion on the rotational parabolic surface, from the base to the tip, it becomes tapered toward the end.

The number of convex portions on the outer surface of the metal portion per one metal-containing particle is preferably 3 or more, more preferably 5 or more. The upper limit of the number of the said convex parts is not specifically limited. The upper limit of the number of convex portions can be appropriately selected in consideration of the particle diameter of the metal-containing particles and the like. In addition, the convex portions included in the metal-containing particles may not be needle-shaped tapering toward the tip, and all of the convex portions included in the metal-containing particles do not need to be needle-shaped tapering toward the tip.

The ratio of the number of acicular convex portions tapering toward the tip to the number of convex portions included per one metal-containing particle is preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, Especially preferably, it is 70 % or more, Especially preferably, it is 80 % or more. The greater the ratio of the number of needle-shaped convex portions, the more effectively the effect of the needle-shaped convex portions is obtained.

The ratio (X) of the surface area of the convex portion among 100% of the total surface area of the outer surface of the metal part is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, and preferably It is 90 % or less, More preferably, it is 80 % or less, More preferably, it is 70 % or less. The greater the ratio of the surface area of the convex portion, the more effectively the effect due to the projection on the convex portion is obtained.

From the viewpoint of effectively improving the connection reliability, the ratio of the surface area of the needle-shaped convex portion to 100% of the total surface area of the outer surface of the metal part is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more. % or more, preferably 90% or less, more preferably 80% or less, still more preferably 70% or less. The greater the ratio of the surface area of the needle-like convex portion, the more effectively the effect of the projection on the convex portion is obtained.

The ratio (average height (B)/average height (b)) of the average height (B) of the plurality of projections to the average height (b) of the plurality of projections is preferably 5 or more, more preferably It is 10 or more, Preferably it is 1000 or less, More preferably, it is 800 or less. When the said ratio (average height (B)/average height (b)) is more than the said minimum, connection reliability becomes still higher. When the said ratio (average height B/average height b) is below the said upper limit, a convex part becomes difficult to bend excessively.

It is preferable that the said metal part which has a some said processus|protrusion is formed by the crystal orientation of a metal or an alloy. In addition, in the Example mentioned later, the metal part is formed by the crystal orientation of a metal or an alloy.

From the standpoint to increase the connection reliability effectively, the compression modulus (10% K value) when compressing the metal-containing particles of 10% is preferably 100N / mm ² or more, more preferably 1000N / mm ² or more, preferably 25000N / mm ² or less, and more preferably at 10000N / mm ^2, more preferably at most 8000N / mm ² or less.

The said compressive modulus (10% K value) of the said metal containing particle|grains can be measured as follows.

Using a micro compression tester, the metal-containing particles are compressed with a smooth indenter end face of a circumference (100 µm in diameter, made of diamond) under conditions of 25°C, a compression rate of 0.3 mN/sec, and a maximum test load of 20 mN. At this time, the load value (N) and the compression displacement (mm) are measured. From the obtained measured value, the said compressive elastic modulus can be calculated|required by a following formula. As said micro compression tester, "Fischer Scope H-100" by a Fischer company etc. is used, for example.

10% K value (N/mm ² )= (3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2

F: Load value (N) when metal-containing particles are compressed by 10%

S: Compressive displacement (mm) when metal-containing particles compressively deform 10%

R: Radius of metal-containing particles (mm)

It is preferable that the ratio of the (111) plane in the X-ray diffraction of the projections is 50% or more.

EMBODIMENT OF THE INVENTION Hereinafter, specific embodiment of this invention is described, referring drawings.

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

As shown in FIG. 1 , the metal-containing particle 1 includes the substrate particle 2 and the metal part 3 .

The metal part 3 is arrange|positioned on the surface of the substrate particle 2. The metal-containing particle|grain 1 is the covering particle|grain by which the surface of the substrate particle 2 was coat|covered with the metal part 3. The metal part 3 is a continuous film.

The metal-containing particle 1 has a plurality of projections 1a on the outer surface of the metal part 3 . The metal part 3 has a plurality of projections 3a on the outer surface. The shape of the plurality of projections 1a, 3a is a needle-shaped tapering toward the end, and in the present embodiment is conical. In this embodiment, the tips of the projections 1a and 3a can be melted at 400°C or less. The metal part 3 has a 1st part and a 2nd part thicker than this 1st part. A portion excluding the plurality of projections 1a and 3a is the first portion of the metal part 3 . The plurality of projections 1a and 3a is the second portion where the thickness of the metal portion 3 is thick.

2 is a cross-sectional view schematically showing metal-containing particles according to a second embodiment of the present invention.

As shown in FIG. 2, 1 A of metal containing particle|grains are equipped with the substrate particle 2 and 3 A of metal parts.

The metal part 3A is arrange|positioned on the surface of the substrate particle 2. The metal-containing particles 1A have a plurality of projections 1Aa on the outer surface of the metal portion 3A. The metal part 3A has a plurality of projections 3Aa on its outer surface. The shape of the plurality of projections 1Aa, 3Aa is a needle-shaped tapering toward the end, and in the present embodiment is a rotational parabolic shape. In this embodiment, the tips of the projections 1Aa and 3Aa can be melted at 400°C or less.

As with the metal-containing particles 1 and 1A, the shape of the plurality of projections on the metal portion is preferably needle-like, tapering toward the tip, and may be conical or parabolic in shape.

3 is a cross-sectional view schematically showing metal-containing particles according to a third embodiment of the present invention.

As shown in FIG. 3, the metal containing particle|grains 1B are equipped with the substrate particle 2 and the metal part 3B.

The metal part 3B is arrange|positioned on the surface of the substrate particle 2. The metal-containing particles 1B have a plurality of projections 1Ba on the outer surface of the metal portion 3B. The metal portion 3B has a plurality of projections 3Ba on its outer surface. The shape of the plurality of projections 1Ba and 3Ba is a partial shape of a sphere. The metal part 3B has metal particles 3BX embedded so that a part thereof is exposed on the outer surface. The part where the metal particle 3BX is exposed constitutes the projections 1Ba and 3Ba. In this embodiment, the tips of the projections 1Ba and 3Ba can be melted at 400°C or less.

As in the case of the metal-containing particles 1B, by making the projections small, the shape of the projections does not need to be a needle-like shape that tapers toward the end, for example, it may be a partial shape of a spherical body.

4 is a cross-sectional view schematically showing metal-containing particles according to a fourth embodiment of the present invention.

As shown in FIG. 4, 1 C of metal containing particle|grains are equipped with the substrate particle 2 and 3 C of metal parts.

The metal-containing particles 1 and the metal-containing particles 1C differ only in the metal portion. That is, in the metal-containing particle 1 , the metal part 3 having a one-layer structure is formed, whereas in the metal-containing particle 1C, the metal part 3C having a two-layer structure is formed.

The metal part 3C has a first metal part 3CA and a second metal part 3CB. 1st, 2nd metal part 3CA, 3CB is arrange|positioned on the surface of the substrate particle 2 . 1st metal part 3CA is arrange|positioned between the substrate particle 2 and 2nd metal part 3CB. Therefore, 1st metal part 3CA is arrange|positioned on the surface of the substrate particle 2, and 2nd metal part 3CB is arrange|positioned on the outer surface of 1st metal part 3CA. The first metal part 3CA has a spherical shape. The metal-containing particles 1C have a plurality of projections 1Ca on the outer surface of the metal part 3C. The metal part 3C has a plurality of projections 3Ca on the outer surface. The second metal part 3CB has a plurality of projections on the outer surface. The shape of the plurality of projections 1Ca and 3Ca is a needle-like tapering end, and in the present embodiment is conical. In this embodiment, the tips of the projections 1Ca and 3Ca can be melted at 400°C or lower. The inner 1st metal part may have a some processus|protrusion on the outer surface.

5 is a cross-sectional view schematically showing metal-containing particles according to a fifth embodiment of the present invention.

As shown in FIG. 5, metal containing particle|grains 1D are equipped with the substrate particle 2 and the metal part 3D.

The metal part 3D is arrange|positioned on the surface of the substrate particle 2. The metal-containing particles 1D have a plurality of projections 1Da on the outer surface of the metal part 3D. The metal-containing particles 1D have a plurality of convex portions (first projections) 3Da on the outer surface of the metal portion 3D. The metal part 3D has a plurality of convex parts (first protrusions) 3Da on the outer surface. The metal portion 3D has a projection 3Db (second projection) smaller than the projection (first projection) 3Da on the outer surface of the projection (first projection) 3Da. The projections (first projections) 3Da and projections 3Db (second projections) are integrated and connected. In the present embodiment, the tip diameter of the projection 3Db (second projection) is small, and the tip of the projection 3Db (second projection) can be melted at 400°C or less.

6 is a cross-sectional view schematically showing metal-containing particles according to a sixth embodiment of the present invention.

As shown in FIG. 6, the metal containing particle|grains 1E are equipped with the substrate particle 2, the metal part 3E, and the core substance 4E.

The metal part 3E is arrange|positioned on the surface of the substrate particle 2. The metal-containing particles 1E have a plurality of projections 1Ea on the outer surface of the metal portion 3E. The metal-containing particles 1E have a plurality of convex portions (first projections) 3Ea on the outer surface of the metal portion 3E. The metal portion 3E has a plurality of convex portions (first projections) 3Ea on its outer surface. The metal part 3E has a projection 3Eb (second projection) smaller than the projection (first projection) 3Ea on the outer surface of the projection (first projection) 3Ea. The projections (first projections) 3Ea and projections 3Eb (second projections) are integrated and connected. In this embodiment, the tip diameter of the projection 3Eb (second projection) is small, and the tip of the projection 3Eb (second projection) can be melted at 400°C or less.

A plurality of core substances 4E are disposed on the outer surface of the substrate particle 2 . The plurality of core materials 4E are disposed inside the metal portion 3E. A plurality of core materials 4E are embedded inside the metal portion 3E. The core material 4E is disposed inside the convex portion 3Ea. The metal portion 3E covers the plurality of core materials 4E. The outer surface of the metal part 3E is raised by the some core substance 4E, and the convex part 3Ea is formed.

Like the metal atom-containing particles 1E, the metal-containing particles may include a plurality of core substances in which the outer surface of the metal portion is raised.

7 is a cross-sectional view schematically showing metal-containing particles according to a seventh embodiment of the present invention.

As shown in FIG. 7, the metal containing particle|grains 1F are equipped with the substrate particle 2 and the metal part 3F.

The metal part 3F is arrange|positioned on the surface of the substrate particle 2. The metal-containing particles 1F have a plurality of projections 1Fa on the outer surface of the metal portion 3F. The metal portion 3F has a projection 3Fb (second projection) smaller than the projection (first projection) 3Fa on the outer surface of the projection (first projection) 3Fa. The projections (first projections) 3Fa and projections 3Fb (second projections) are not integrated. In the present embodiment, the tip diameter of the projection 3Fb (second projection) is small, and the tip of the projection 3Fb (second projection) can be melted at 400°C or less.

8 is a cross-sectional view schematically showing metal-containing particles according to an eighth embodiment of the present invention.

As shown in FIG. 8, metal-containing particle|grains 1G are equipped with the substrate particle 2 and the metal part 3G.

The metal part 3G includes a first metal part 3GA and a second metal part 3GB. 1st, 2nd metal part 3GA, 3GB is arrange|positioned on the surface of the substrate particle 2 . 1st metal part 3GA is arrange|positioned between the substrate particle 2 and 2nd metal part 3GB. Therefore, 1st metal part 3GA is arrange|positioned on the surface of the substrate particle 2, and 2nd metal part 3GB is arrange|positioned on the outer surface of 1st metal part 3GA.

Metal part 3G is arrange|positioned on the surface of the substrate particle 2. The metal-containing particles 1G have a plurality of projections 1Ga on the outer surface of the metal portion 3G. The metal-containing particles 1G have a plurality of convex portions (first projections) 3Ga on the outer surface of the metal portion 3G. The metal portion 3G has a projection 3Gb (second projection) smaller than the projection (first projection) 3Ga on the outer surface of the projection (first projection) 3Ga. An interface exists between the convex portion (first protrusion) 3Ga and the protrusion 3Gb (second protrusion). In the present embodiment, the tip diameter of the projection 3Gb (second projection) is small, and the tip of the projection 3Gb (second projection) can be melted at 400°C or less.

11 to 14, images of actually produced metal-containing particles were shown. The metal-containing particles shown in FIGS. 11 to 14 have a plurality of projections on the outer surface of the metal portion, and the tips of the plurality of projections can be melted at 400°C or lower. In the metal-containing particle|grains shown in FIG. 14, a metal part has a some convex part on the outer surface, and has a processus|protrusion smaller than the said convex part on the outer surface of this convex part.

Also, Figs. 15 to 18 show images of the particles obtained by melting and then solidifying the projections of the metal parts of the prepared metal-containing particles. Fig. 18 is a particle obtained by melting and then solidifying the tip of the projection of the metal part of the metal-containing particle shown in Fig. 14 .

Hereinafter, the metal-containing particles will be described in more detail. In addition, in the following description, "(meth)acryl" means one or both of "acryl" and "methacryl", and "(meth)acrylate" is one of "acrylate" and "methacrylate" or both.

[substrate particles]

As said substrate particle, a resin particle, the inorganic particle except a metal particle, organic-inorganic hybrid particle|grains, a metal particle, etc. are mentioned. The said substrate particle may have a core and the shell arrange|positioned on the surface of this core, and core-shell particle|grains may be sufficient as it. It is preferable that it is a substrate particle except a metal particle, and, as for the said substrate particle, it is more preferable that they are an inorganic particle or organic-inorganic hybrid particle|grains except a resin particle and a metal particle.

As for the said substrate particle, it is more preferable that they are a resin particle or organic-inorganic hybrid particle|grains, and a resin particle may be sufficient as it, and an organic-inorganic hybrid particle|grain may be sufficient as it. By use of these preferable substrate particles, the metal-containing particle|grains suitable for the connection use of two connection object members are obtained.

When the said substrate particle is a resin particle or organic-inorganic hybrid particle|grains, the said metal containing particle|grains are easy to deform|transform, and the softness|flexibility of the said metal containing particle|grains becomes high. For this reason, the shock absorption property becomes high after connection.

As resin for forming the said resin particle, various organic substances are used suitably. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Polyalkylreterephthalate, 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, polyetheretherketone, polyethersulfone and various polymerizable monomers having an ethylenically unsaturated group. The polymer obtained by making it superpose|polymerize 1 type or 2 or more types, etc. are mentioned. Since it is possible to design and synthesize resin particles having any physical properties at the time of compression suitable for the connection use of the two connection object members, and the hardness of the substrate particles can be easily controlled within a suitable range, the resin particles are formed It is preferable that resin for this is the polymer which polymerized 1 type(s) or 2 or more types of polymerizable monomers which have a plurality of ethylenically unsaturated groups.

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

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 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; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; 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.

Examples of the crosslinkable monomer include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanedi(meth)acrylate, and trimethylolpropane tri(meth)acryl. Rate, 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 rate, (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) acryloxypropyl trimethoxysilane, trimethoxysilyl styrene and silane-containing monomers such as vinyltrimethoxysilane.

The said resin particle can be obtained by superposing|polymerizing the polymeric 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, the method of superposing|polymerizing by swelling a monomer with a radical polymerization initiator using non-crosslinked seed particle|grains, etc. are mentioned, for example.

When the said substrate particle is the inorganic particle or organic-inorganic hybrid particle|grains except a metal particle, a silica, an alumina, barium titanate, a zirconia, carbon black, etc. are mentioned as an inorganic substance for forming the said substrate particle. Preferably, the inorganic material is not a metal. Although it does not specifically limit as particle|grains formed of the said silica, For example, after hydrolyzing the silicon compound which has two or more hydrolysable alkoxysilyl groups to form crosslinked polymer particles, the particle|grains obtained by performing baking as needed are mentioned. have. As said organic-inorganic hybrid particle|grains, the organic-inorganic hybrid particle|grains etc. which were formed of the crosslinked alkoxysilyl polymer and an acrylic resin are mentioned, for example.

It is preferable that the said organic-inorganic hybrid particle is a core-shell type organic-inorganic hybrid particle which has a core and the shell arrange|positioned on the surface of the said core. It is preferable that the said core is an organic core. It is preferable that the said shell is an inorganic shell. It is preferable that the said substrate particle is an organic-inorganic hybrid particle|grain which has an organic core and the inorganic shell arrange|positioned on the surface of the said organic core from a viewpoint of improving connection reliability effectively.

As a material for forming the said inorganic shell, the inorganic substance for forming the above-mentioned substrate particle is mentioned. It is preferable that the material for forming the said inorganic shell is silica. It is preferable that the said inorganic shell is formed by making a metal alkoxide into a shell-like thing by a sol-gel method, and then baking the said shell-like thing 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 a silane alkoxide.

The particle diameter of the core is preferably 0.5 µm or more, more preferably 1 µm or more, preferably 500 µm or less, more preferably 100 µm or less, still more preferably 50 µm or less, particularly preferably 20 µm or less. or less, most preferably 10 µm or less. When the particle diameter of the said core is more than the said minimum and below the said upper limit, it becomes possible to use suitably for the connection use of two connection object members. For example, if the particle size of the core is equal to or greater than the lower limit and equal to or less than the upper limit, when two connection object members are connected using the metal-containing particles, the contact area between the metal-containing particles and the connection object member is sufficiently large, Moreover, when forming a metal part, it becomes difficult to form the aggregated metal containing particle|grains. Moreover, the space|interval of two connection object members connected via metal containing particle|grains does not become large too much, and a metal part becomes difficult to peel from the surface of a substrate particle.

The particle diameter of the core means a diameter when the core has a true spherical shape, and means a maximum diameter when the core has a shape other than a true spherical shape. In addition, the particle diameter of a core means the average particle diameter which measured the core with arbitrary particle diameter measuring apparatuses. For example, the particle size distribution analyzer using principles, such as laser light scattering, a change in electrical resistance value, and image analysis after imaging, can be used.

The thickness of the shell is preferably 100 nm or more, more preferably 200 nm or more, preferably 5 µm or less, more preferably 3 µm or less. If the thickness of the said shell is more than the said minimum and below the said upper limit, it becomes possible to use suitably for the connection use of two connection object members. The thickness of the said shell is an average thickness per one substrate particle. The thickness of the shell can be controlled by controlling the sol-gel method.

When the said substrate particle is a metal particle, silver, copper, nickel, a silicon, gold, titanium, etc. are mentioned as a metal for forming 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 0.1 micrometer or more, More preferably, it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more, More preferably, it is 1.5 micrometer or more, Especially preferably, it is 2 micrometers or more, Preferably is 1000 µm or less, more preferably 500 µm or less, still more preferably 400 µm or less, still more preferably 100 µm or less, still more preferably 50 µm or less, still more preferably 30 µm or less, particularly preferably is 5 μm or less, most preferably 3 μm or less. Connection reliability becomes it still higher that the particle diameter of the said substrate particle is more than the said minimum. Moreover, when forming a metal part by electroless-plating on the surface of a substrate particle, it becomes difficult to aggregate, and it becomes difficult to form the aggregated metal containing particle|grains. If the average particle diameter of a substrate particle is below the said upper limit, it is easy to fully compress a metal containing particle, and connection reliability becomes still higher.

When a substrate particle is a true spherical shape, the particle diameter of the said substrate particle shows a diameter, and, when a substrate particle is not a true spherical shape, it shows a largest diameter.

From a viewpoint of further suppressing generation|occurrence|production of the crack or peeling of the connection part in the heat cycle test of connection reliability, and suppressing generation|occurrence|production of the crack at the time of stress load further, the said substrate particle is particle|grains (silicon particle) containing a silicone resin It is preferable to be It is preferable that the material of the said substrate particle contains a silicone resin.

The material of the silicon particles is preferably a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms, a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms, or a radical polymerizable group It is preferable that it is a silane compound which has at both terminals. When these materials are reacted, siloxane bonds are formed. In the silicon particle obtained, a radically polymerizable group and a C5 or more hydrophobic group generally remain|survive. By using such a material, silicon particles having a primary particle diameter of 0.1 µm or more and 500 µm or less can be easily obtained, and chemical resistance of the silicon particles can be improved, and moisture permeability can be lowered.

In the silane compound which has the said radically polymerizable group, it is preferable that the radically polymerizable group is couple|bonded with the silicon atom directly. As for the silane compound which has the said radically polymerizable group, only 1 type may be used and 2 or more types may be used together.

It is preferable that the silane compound which has the said radically polymerizable group is an alkoxysilane compound. Examples of the silane compound having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, divinylmethoxyvinylsilane, divinylethoxyvinylsilane, and divinyl. Dimethoxysilane, divinyl diethoxysilane, 1, 3- divinyl tetramethyl disiloxane, etc. are mentioned.

In the silane compound having a hydrophobic group having 5 or more carbon atoms, the hydrophobic group having 5 or more carbon atoms is preferably directly bonded to a silicon atom. As for the silane compound which has the said C5 or more hydrophobic group, only 1 type may be used and 2 or more types may be used together.

It is preferable that the said silane compound which has a C5 or more hydrophobic group is an alkoxysilane compound. Examples of the silane compound having a hydrophobic group having 5 or more carbon atoms include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, dimethylmethoxyphenylsilane, dimethylethoxyphenylsilane, hexaphenyldisiloxane, 1,3,3, 5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, hexaphenylcyclotrisiloxane, phenyltris ( trimethylsiloxy)silane, octaphenylcyclotetrasiloxane, and the like.

In the silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms, the radical polymerizable group is preferably directly bonded to a silicon atom, and the hydrophobic group having 5 or more carbon atoms is preferably directly bonded to a silicon atom. As for the silane compound which has the said radically polymerizable group and has a C5 or more hydrophobic group, only 1 type may be used and 2 or more types may be used together.

Examples of the silane compound having a radical polymerizable group and having a hydrophobic group having 5 or more carbon atoms include phenylvinyldimethoxysilane, phenylvinylethoxysilane, phenylmethylvinylmethoxysilane, phenylmethylvinylethoxysilane, and diphenylvinylmethoxysilane. , diphenylvinylethoxysilane, phenyldivinylmethoxysilane, phenyldivinylethoxysilane, and 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane.

When using the silane compound having a radical polymerizable group and the silane compound having a hydrophobic group having 5 or more carbon atoms to obtain silicon particles, the silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms Silver is preferably used in a weight ratio of 1:1 to 1:20, and more preferably 1:5 to 1:15.

The whole silane compound for obtaining a silicone particle WHEREIN: It is preferable that it is 1:0.5 - 1:20, and, as for the number of radically polymerizable groups and the number of C5 or more hydrophobic groups, it is more preferable that they are 1:1 - 1:15.

From the viewpoint of effectively increasing chemical resistance, effectively lowering moisture permeability, and controlling the 10% K value to a suitable range, the silicone particle preferably has a dimethylsiloxane skeleton in which two methyl groups are bonded to one silicon atom, the silicone particle The material preferably contains a silane compound in which two methyl groups are bonded to one silicon atom.

From the viewpoint of effectively increasing chemical resistance, effectively lowering moisture permeability, and controlling the 10% K value within a suitable range, it is preferable that the silicon particles react with the above-mentioned silane compound with a radical polymerization initiator to form a siloxane bond. . In general, using a radical polymerization initiator, it is difficult to obtain silicon particles having a primary particle diameter of 0.1 µm or more and 500 µm or less, and it is particularly difficult to obtain silicon particles having a primary particle diameter of 100 µm or less. In contrast, even when a radical polymerization initiator is used, silicon particles having a primary particle diameter of 0.1 μm or more and 500 μm or less can be obtained by using the silane compound, and silicon particles having a primary particle diameter of 100 μm or less. can also get

In order to obtain the silicon particles, it is not necessary to use a silane compound having a hydrogen atom bonded to a silicon atom. In this case, the silane compound can be polymerized using a radical polymerization initiator without using a metal catalyst. As a result, it is possible to prevent the silicon particles from containing the metal catalyst, the content of the metal catalyst in the silicon particles can be reduced, chemical resistance can be effectively increased, moisture permeability can be effectively lowered, and the 10% K value can be brought into a suitable range. can be controlled

Specific examples of the method for producing the silicone particles include a method of producing silicone particles by performing a polymerization reaction of a silane compound by a suspension polymerization method, a dispersion polymerization method, a mini-emulsion polymerization method, an emulsion polymerization method, or the like. After the polymerization of the silane compound is advanced to obtain an oligomer, a polymerization reaction of the silane compound as a polymer (oligomer, etc.) may be performed by suspension polymerization, dispersion polymerization, mini-emulsion polymerization, emulsion polymerization, etc. to produce silicone particles. . For example, you may polymerize the silane compound which has a vinyl group, and you may obtain the silane compound which has the vinyl group couple|bonded with the silicon atom at the terminal. You may polymerize the silane compound which has a phenyl group, and may obtain the silane compound which has the phenyl group couple|bonded with the silicon atom in the side chain as a polymer (oligomer etc.). A silane compound having a vinyl group and a silane compound having a phenyl group are polymerized to obtain a silane compound having a vinyl group bonded to a silicon atom at the terminal and a phenyl group bonded to a silicon atom in a side chain as a polymer (oligomer, etc.).

The silicon particle may have a some particle|grain on the outer surface. In this case, a silicon particle may be equipped with a silicon particle main body, and the some particle|grain arrange|positioned on the surface of a silicon particle main body. As said some particle|grains, a silicon particle, a spherical silica, etc. are mentioned. Aggregation of silicon particles can be suppressed by the presence of the plurality of particles.

[Metal part]

The tip of the protrusion of the metal part can be melted at 400° C. or less. From the viewpoint of suppressing the consumption of energy during heating by lowering the melting temperature and suppressing thermal deterioration of the member to be connected, etc., it is preferable that the tip of the projection of the metal part can be melted at 350 ° C. or less, and 300 ° C. or less It is more preferable that it can be melted at a temperature of 250°C or less, and it is particularly preferable that it can be melted at 200°C or less. The melting temperature of the tip of the projection can be controlled by the type of metal at the tip of the projection and the shape of the tip of the projection. The melting point of the base of the convex portion, the central position of the height of the projection, the base of the projection, and the central position of the height of the projection may exceed 200°C, may exceed 250°C, or exceed 300°C It may be over 350 degreeC, and may exceed 400 degreeC. The said metal part, the said convex part, and the said processus|protrusion may have a part exceeding 200 degreeC, may have a part exceeding 250 degreeC, may have a part exceeding 300 degreeC, and exceeding 350 degreeC. You may have a part and may have a part exceeding 400 degreeC.

The material of the said metal part is not specifically limited. The material of the metal part preferably includes a metal. Examples of the metal include gold, silver, palladium, rhodium, iridium, lithium, copper, platinum, zinc, iron, tin, lead, ruthenium, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, and thallium. , germanium, cadmium, silicon, and alloys thereof. Moreover, as said metal, tin-doped indium oxide (ITO), etc. are mentioned.

In the present invention, the material of the metal part is selected so that the tip of the projection of the metal part can be melted at 400° C. or less.

From the viewpoint of effectively improving the connection reliability, the material of the projections preferably contains silver, copper, gold, palladium, tin, indium or zinc. The material of the said projection does not need to contain tin.

It is preferable that the material of the metal part is not solder. Since the material of the metal part is not solder, it is possible to suppress excessive melting of the entire metal part. The material of the metal part does not need to contain tin.

From the viewpoint of effectively increasing the connection reliability, the material of the metal part includes silver, copper, gold, palladium, tin, indium, zinc, nickel, cobalt, iron, tungsten, molybdenum, ruthenium, platinum, rhodium, iridium, phosphorus or boron. It is preferable that silver, copper, gold, palladium, tin, indium or zinc are included, and it is more preferable that silver is included. As for these preferable materials, only 1 type may be used and 2 or more types may be used together. From a viewpoint of improving connection reliability effectively, the said silver may be contained as silver single-piece|unit or silver oxide. Examples of silver oxide include Ag ₂ O and AgO.

In 100 weight% of the metal parts containing silver, content of silver becomes like this. Preferably it is 0.1 weight% or more, More preferably, it is 1 weight% or more, Preferably it is 100 weight% or less, More preferably, it is 90 weight% or less, 80 weight% or less. Weight % or less may be sufficient, 60 weight% or less may be sufficient, 40 weight% or less may be sufficient, 20 weight% or less may be sufficient, and 10 weight% or less may be sufficient. When content of silver is more than the said minimum and below the said upper limit, bonding strength will become high and connection reliability will become still higher.

The said copper may be contained as a copper single-piece|unit or copper oxide.

In 100 weight% of metal parts containing copper, content of copper becomes like this. Preferably it is 0.1 weight% or more, More preferably, it is 1 weight% or more, Preferably it is 100 weight% or less, More preferably, it is 90 weight% or less, 80 weight% or less may be sufficient, 60 weight% or less may be sufficient, 40 weight% or less may be sufficient, 20 weight% or less may be sufficient, and 10 weight% or less may be sufficient. Bonding strength becomes it high that content of copper is more than the said minimum and below the said upper limit, and connection reliability becomes still higher.

The said metal part may be formed by one layer. The said metal part may be formed of several layers.

The outer surface of the said metal part may be antirust-treated. The said metal-containing particle|grains may have a rust prevention film on the outer surface of the said metal part. Examples of the rust prevention treatment include a method of disposing a rust inhibitor on the outer surface of the metal portion, a method of alloying the outer surface of the metal portion to improve corrosion resistance, a method of coating a highly corrosion-resistant metal film on the outer surface of the metal portion, and the like. As said rust preventive agent, Nitrogen-containing heterocyclic compounds, such as a benzotriazole compound and an imidazole compound; sulfur-containing compounds such as mercaptan compounds, thiazole compounds, and organic disulfide compounds; Phosphorus containing compounds, such as an organophosphoric acid compound, are mentioned.

[Anti-rust treatment]

In order to suppress the corrosion of metal-containing particles and to lower the connection resistance between the electrodes, it is preferable that the outer surface of the metal portion is subjected to an antirust treatment or a sulfurization treatment.

Examples of the sulfurizing agent, rust inhibitor, and discoloration inhibitor include nitrogen-containing heterocyclic compounds such as benzotriazole compounds and imidazole compounds; sulfur-containing compounds such as mercaptan compounds, thiazole compounds, and organic disulfide compounds; Phosphorus containing compounds, such as an organophosphoric acid compound, are mentioned.

From a viewpoint of further improving the conduction reliability, it is preferable that the outer surface of the metal part is subjected to a rust prevention treatment with a compound having an alkyl group having 6 to 22 carbon atoms. The surface of the said metal part may be rust-preventive-treated with the compound which does not contain phosphorus, and has a C6-C22 alkyl group and may be rust-preventive-treated with the compound which does not contain phosphorus. From the viewpoint of further improving the conduction reliability, it is preferable that the outer surface of the metal part is subjected to a rust prevention treatment with an alkyl phosphate compound or an alkyl thiol. An anti-rust film can be formed on the outer surface of the metal part by the anti-rust treatment.

It is preferable that the said rust preventive film is formed of the compound (henceforth referred to as compound A) which has a C6-C22 alkyl group. It is preferable that the outer surface of the said metal part is surface-treated with the said compound A. When carbon number of the said alkyl group is 6 or more, it becomes it more difficult to generate|occur|produce rust in the whole metal part. When carbon number of the said alkyl group is 22 or less, the electroconductivity of a metal containing particle|grains will become high. It is preferable that carbon number of the said alkyl group in the said compound A is 16 or less from a viewpoint of improving the electroconductivity of metal containing particle|grains further. The said alkyl group may have a linear structure and may have a branched structure. It is preferable that the said alkyl group has a linear structure.

The said compound A will not be specifically limited if it has a C6-C22 alkyl group. The compound A is a phosphate ester or salt having an alkyl group having 6 to 22 carbon atoms, a phosphite ester or salt thereof having an alkyl group having 6 to 22 carbon atoms, an alkoxysilane having an alkyl group having 6 to 22 carbon atoms, an alkyl group having 6 to 22 carbon atoms. It is preferable that it is an alkylthiol which has, or a dialkyl disulfide which has a C6-C22 alkyl group. That is, the compound A having an alkyl group having 6 to 22 carbon atoms is preferably a phosphoric acid ester or a salt thereof, a phosphorous acid ester or a salt thereof, an alkoxysilane, an alkylthiol, or a dialkyl disulfide. By use of these preferable compound A, it can make it difficult to generate|occur|produce further rust in a metal part. From the viewpoint of making rust more difficult to occur, the compound A is preferably the phosphate ester or a salt thereof, a phosphite ester or a salt thereof, or an alkylthiol, and more preferably the phosphate ester or a salt thereof, or a phosphite ester or a salt thereof. desirable. As for the said compound A, only 1 type may be used and 2 or more types may be used together.

The compound A preferably has a reactive functional group capable of reacting with the outer surface of the metal part. When the metal-containing particles include an insulating material disposed on the outer surface of the metal part, the compound A preferably has a reactive functional group capable of reacting with the insulating material. It is preferable that the rust preventive film is chemically bonded to the metal part. It is preferable that the rust preventive film is chemically bonded to the insulating material. It is more preferable that the rust preventive film is chemically bonded to both the metal part and the insulating material. Due to the presence of the reactive functional group and the chemical bonding, peeling of the rust preventive film is difficult to occur, and as a result, rust is more difficult to occur in the metal part, and the insulating material is not intended from the surface of the metal-containing particles. It becomes more difficult to detach.

Examples of the phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof include phosphate hexyl ester, phosphate heptyl ester, phosphate monooctyl ester, phosphate monononyl ester, phosphate monodecyl ester, phosphate monoundecyl ester, and monophosphate ester. Dodecyl ester, phosphoric acid monotridecyl ester, phosphoric acid monotetradecyl ester, phosphoric acid monopentadecyl ester, phosphoric acid monohexyl ester monosodium salt, phosphoric acid monoheptyl ester monosodium salt, phosphoric acid monooctyl ester monosodium salt, phosphoric acid monononyl ester Monosodium phosphate, monosodium phosphate monodecyl ester, monosodium phosphate monoundecyl ester, monosodium phosphate monododecyl ester, monosodium phosphate monotridecyl ester, monosodium phosphate monotetradecyl ester, and monosodium phosphate monotetradecyl ester A pentadecyl ester monosodium salt etc. are mentioned. You may use the potassium salt of the said phosphoric acid ester.

As the phosphorous acid ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof, for example, hexyl phosphite, heptyl phosphite, monooctyl phosphite, monononyl phosphite, monodecyl phosphite, monoundecyl phosphite; Phosphorous acid monododecyl ester, phosphorous acid monotridecyl ester, phosphorous acid monotetradecyl ester, phosphorous acid monopentadecyl ester, phosphorous acid monohexyl ester monosodium salt, phosphorous acid monoheptyl ester monosodium salt, phosphorous acid monooctyl ester monosodium salt, phosphorus Monosodium acid monononyl ester, monosodium phosphite monodecyl ester, monosodium phosphite monoundecyl ester, monosodium phosphite monododecyl ester, monosodium phosphite monotridecyl ester, monosodium phosphite monotetradecyl ester salts, and monosodium phosphorous acid monopentadecyl ester salts; and the like. You may use the potassium salt of the said phosphite.

Examples of the alkoxysilane having an alkyl group having 6 to 22 carbon atoms include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxy Silane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltri and ethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane and pentadecyltriethoxysilane. .

Examples of the alkylthiol having an alkyl group having 6 to 22 carbon atoms include hexylthiol, heptylthiol, octylthiol, nonylthiol, decylthiol, undecylthiol, dodecylthiol, tridecylthiol, tetradecylthiol, and pentadecylthiol. and hexadecylthiol. The alkylthiol preferably has a thiol group at the terminal of the alkyl chain.

Examples of the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms include dihexyldisulfide, diheptyldisulfide, dioctyldisulfide, dinonyldisulfide, didecyldisulfide, diundecyldisulfide, dido Decyl disulfide, ditridecyl disulfide, ditetradecyl disulfide, dipentadecyl disulfide, dihexadecyl disulfide, etc. are mentioned.

From the viewpoint of further improving the conduction reliability, the outer surface of the metal part is subjected to sulfur-resistance treatment with any layer of a sulfur-containing compound containing a sulfide compound or a thiol compound as a main component, a benzotriazole compound, or a polyoxyethylene ether surfactant. It is preferable to have An anti-rust film can be formed on the outer surface of the metal part by the sulfiding treatment.

Examples of the sulfide compound include 6 to 40 carbon atoms, such as dihexyl sulfide, diheptyl sulfide, dioctyl sulfide, didecyl sulfide, didodecyl sulfide, ditetradecyl sulfide, dihexadecyl sulfide, and dioctadecyl sulfide. linear or branched dialkyl sulfide (alkyl sulfide) having a degree (preferably about 10 to 40 carbon atoms); aromatic sulfides having about 12 to 30 carbon atoms, such as diphenyl sulfide, phenyl-p-tolyl sulfide, and 4,4-thiobisbenzenethiol; Thiodicarboxylic acids, such as 3,3'- thiodipropionic acid and 4,4'- thiodibutanoic acid, etc. are mentioned. It is especially preferable that the said sulfide compound is a dialkyl sulfide.

Examples of the thiol compound include about 4 to 40 carbon atoms such as 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-methyl-2-propanethiol and octadecylthiol (more Preferably about 6-20) linear or branched alkylthiol etc. are mentioned. Moreover, the compound etc. which the hydrogen atom couple|bonded with the carbon group of these compounds were substituted with fluorine are mentioned.

As said benzotriazole compound, benzotriazole, a benzotriazole salt, methylbenzotriazole, carboxybenzotriazole, a benzotriazole derivative, etc. are mentioned.

In addition, as said discoloration inhibitor, the brand name "AC-20", "AC-70", "AC-80" manufactured by Kitaike Sangyo Co., Ltd., the brand name "Ntech CU-56" manufactured by Meltex Corporation, the brand name of Yamato Kasei Co., Ltd. "New Dyne Silver", "New Dyne Silver S-1", the brand name "B-1057" by Chiyoda Chemical Co., Ltd., and the brand name "B-1009NS" by the Chiyoda Chemical Company, etc. are mentioned.

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

The following method is mentioned as a method of forming the processus|protrusion which has a needle-like shape tapering toward the end on the outer surface of a metal part.

Method by electroless high-purity nickel plating using hydrazine as reducing agent, method by electroless palladium-nickel alloy using hydrazine as reducing agent, electroless CoNiP alloy plating method using hypophosphorous acid as reducing agent, electroless plating using hydrazine as reducing agent The method by silver plating, the method by electroless copper- nickel- phosphorus alloy plating using a hypophosphorous acid compound as a reducing agent, etc. are mentioned.

In the method of forming by electroless plating, a catalytic process and an electroless plating process are generally performed. Hereinafter, an example of a method of forming an alloy plating layer containing copper and nickel on the surface of a resin particle by electroless plating and a projection having a needle-like shape tapering toward the end on the outer surface of the metal part will be described.

In the said catalysis process, the catalyst used as the starting point for forming a plating layer by electroless-plating is formed in the surface of a resin particle.

As a method of forming the catalyst on the surface of the resin particles, for example, after adding the resin particles to a solution containing palladium chloride and tin chloride, the surface of the resin particles is activated with an acid solution or an alkali solution, and the resin particles A method of depositing palladium on the surface of and how to do it. As the reducing agent, a phosphorus-containing reducing agent is used. In addition, as the reducing agent, a metal portion containing phosphorus can be formed by using a phosphorus-containing reducing agent.

In the electroless plating process, in the electroless copper-nickel-phosphorus alloy plating method using a plating solution containing a copper-containing compound, a complexing agent, and a reducing agent, a hypophosphorous acid compound is included as a reducing agent, and the reducing agent is a reaction initiating metal catalyst It is preferable to use a copper-nickel-phosphorus alloy plating solution containing a nickel-containing compound and a nonionic surfactant.

By immersing the resin particles in a copper-nickel-phosphorus alloy plating bath, the catalyst can precipitate a copper-nickel-phosphorus alloy on the surface of the resin particles formed on the surface, and form a metal part containing copper, nickel and phosphorus have.

Copper sulfate, cupric chloride, copper nitrate, etc. are mentioned as said copper-containing compound. It is preferable that the said copper-containing compound is copper sulfate.

Examples of the nickel-containing compound include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate. The nickel-containing compound is preferably nickel sulfate.

As said phosphorus containing reducing agent, hypophosphorous acid, sodium hypophosphite, etc. are mentioned. In addition to the phosphorus-containing reducing agent, a boron-containing reducing agent may be used. As said boron-containing reducing agent, dimethylamine borane, sodium borohydride, potassium borohydride, etc. are mentioned.

The complexing agent is a monocarboxylic acid complexing agent such as sodium acetate and sodium propionate, a dicarboxylic acid complexing agent such as disodium malonate, a tricarboxylic acid complexing agent such as disodium succinate, lactic acid, DL-malic acid, and Rochelle salt , a hydroxy acid complexing agent such as sodium citrate and sodium gluconate, an amino acid complexing agent such as glycine and EDTA, an amine complexing agent such as ethylenediamine, an organic acid complexing agent such as maleic acid, or a salt thereof. Only 1 type may be used for these preferable complexing agents, and 2 or more types may be used together.

As said surfactant, anionic surfactant, cationic surfactant, nonionic surfactant, or amphoteric surfactant is mentioned, Especially a nonionic surfactant is suitable. Preferred nonionic surfactants are polyethers comprising ether oxygen atoms. Preferred nonionic surfactants include polyoxyethylene lauryl ether, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene alkylamine and polyoxyalkylene adducts of ethylenediamine. Preferably, they are polyoxyethylene monoalkyl ether, such as polyoxyethylene monobutyl ether, polyoxypropylene monobutyl ether, and polyoxyethylene polyoxypropylene glycol monobutyl ether, polyethyleneglycol, or phenol ethoxylate. As for the said surfactant, only 1 type may be used and 2 or more types may be used together. Polyethylene glycol having a molecular weight of about 1000 (eg, 500 or more and 2000 or less) is particularly preferable.

In order to form the protrusions having a needle-like shape tapering toward the end on the outer surface of the metal part, it is preferable to control the molar ratio of the copper compound to the nickel compound. The amount of the copper compound used is preferably 2 to 100 times the molar ratio of the nickel compound.

Moreover, even if it does not use the said nonionic surfactant etc., the processus|protrusion which has a needle-like shape is obtained. In order to form a protrusion having a sharper apex angle and a tapering shape, it is preferable to use a nonionic surfactant, and it is particularly preferable to use polyethylene glycol having a molecular weight of about 1000 (eg, 500 or more and 2000 or less). desirable.

The ratio (average height (b)/average diameter (c)) of the average height (b) of the plurality of projections to the average diameter (c) of the bases of the plurality of projections depends on the thickness of the metal part, and can be controlled by the immersion time of The plating temperature is preferably 30°C or higher, preferably 100°C or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.

Next, an example of a method of forming projections having a needle-like shape tapering toward the end on the outer surface of the silver plating layer and the metal portion on the surface of the resin particles by electroless plating will be described.

In the said catalysis process, the catalyst used as the starting point for forming a plating layer by electroless-plating is formed in the surface of a resin particle.

As a method of forming the catalyst on the surface of the resin particle, for example, after adding the resin particle to a solution containing palladium chloride and tin chloride, the surface of the resin particle is activated with an acid solution or an alkali solution, and the resin particle A method of depositing palladium on the surface of and how to do it. As the reducing agent, a phosphorus-containing reducing agent is used. In addition, as the reducing agent, a metal portion containing phosphorus can be formed by using a phosphorus-containing reducing agent.

In the electroless plating process, in the electroless silver plating method using a plating solution containing a silver-containing compound, a complexing agent, and a reducing agent, a silver plating solution containing hydrazine, a nonionic surfactant and a sulfur-containing organic compound as a reducing agent is used It is preferable to do

By immersing a resin particle in a silver plating bath, a catalyst can make silver precipitate on the surface of the resin particle formed in the surface, and can form the metal part containing silver.

As said silver containing compound, potassium silver cyanide, silver nitrate, silver sodium thiosulfate, silver gluconate, a silver-cysteine complex, and silver methanesulfonate are preferable.

As said reducing agent, hydrazine, sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, formalin, glucose, etc. are mentioned.

As the reducing agent for forming the needle-like projections, hydrazine monohydrate, hydrazine hydrochloride and hydrazine sulfate are preferable.

The complexing agent is a monocarboxylic acid complexing agent such as sodium acetate and sodium propionate, a dicarboxylic acid complexing agent such as disodium malonate, a tricarboxylic acid complexing agent such as disodium succinate, lactic acid, DL-malic acid, and Rochelle salt , a hydroxy acid-based complexing agent such as sodium citrate and sodium gluconate, an amino acid-based complexing agent such as glycine and EDTA, an amine-based complexing agent such as ethylenediamine, an organic acid-based complexing agent such as maleic acid, or a salt thereof . Only 1 type may be used for these preferable complexing agents, and 2 or more types may be used together.

As said surfactant, anionic surfactant, cationic surfactant, nonionic surfactant, or amphoteric surfactant is mentioned, Especially a nonionic surfactant is suitable. Preferred nonionic surfactants are polyethers comprising ether oxygen atoms. Preferred nonionic surfactants include polyoxyethylene lauryl ether, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene alkylamine and polyoxyalkylene adducts of ethylenediamine. Preferably, they are polyoxyethylene monoalkyl ether, such as polyoxyethylene monobutyl ether, polyoxypropylene monobutyl ether, and polyoxyethylene polyoxypropylene glycol monobutyl ether, polyethylene glycol, or phenol ethoxylate. As for the said surfactant, only 1 type may be used and 2 or more types may be used together. Polyethylene glycol having a molecular weight of about 1000 (eg, 500 or more and 2000 or less) is particularly preferable.

Moreover, even if it does not use the said nonionic surfactant etc., the processus|protrusion which has a needle-like shape is obtained. In order to form a protrusion having a sharper apex angle and a tapering shape, it is preferable to use a nonionic surfactant, and it is particularly preferable to use polyethylene glycol having a molecular weight of about 1000 (eg, 500 or more and 2000 or less). desirable.

Examples of the sulfur-containing organic compound include an organic compound having a sulfide or sulfonic acid group, a thiourea compound, and a benzothiazole compound. Examples of the organic compound having a sulfide or sulfonic acid group include N,N-dimethyl-dithiocarbamic acid-(3-sulfopropyl)ester, 3-mercapto-propylsulfonic acid-(3-sulfopropyl)ester, 3-mercapto -Propylsulfonate sodium salt, 3-mercapto-1-propanesulfonic acid potassium salt, carbonic acid-dithio-o-ethyl ester, bissulfopropyldisulfide, bis-(3-sulfopropyl)-disulfide/disodium salt; 3-(benzothiazolyl-s-thio)propylsulfonate sodium salt, pyridiniumpropylsulfobetaine, 1-sodium-3-mercaptopropane-1-sulfonate, N,N-dimethyl-dithiocarbamic acid-( 3-sulfoethyl) ester, 3-mercapto-ethyl propylsulfonic acid-(3-sulfoethyl) ester, 3-mercapto-ethylsulfonic acid sodium salt, 3-mercapto-1-ethanesulfonic acid potassium salt, carbonic acid-dithio -o-ethyl ester-s-ester, bissulfoethyldisulfide, 3-(benzothiazolyl-s-thio)ethylsulfonate sodium salt, pyridinium ethylsulfobetaine, 1-sodium-3-mercaptoethane-1 - A sulfonate, a thiourea compound, etc. are mentioned. Examples of the thiourea compound include thiourea, 1,3-dimethylthiourea, trimethylthiourea, diethylthiourea, and allylthiourea.

Moreover, even if it does not use the said sulfur containing organic compound etc., the processus|protrusion which has a needle-like shape is obtained. In order to form a protrusion having a sharper apex angle and a tapering shape, it is preferable to use a sulfur-containing organic compound, and it is particularly preferable to use thiourea.

The ratio (average height (b)/average diameter (c)) of the average height (b) of the plurality of projections to the average diameter (c) of the bases of the plurality of projections depends on the thickness of the metal part, and can be controlled by the immersion time of The plating temperature is preferably 30°C or higher, preferably 100°C or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.

Next, an example of a method of forming a high-purity nickel plating layer on the surface of a resin particle by electroless plating and a projection having a needle-like shape tapering toward the end on the outer surface of the metal part will be described.

In the said catalysis process, the catalyst used as the starting point for forming a plating layer by electroless-plating is formed in the surface of a resin particle.

As a method of forming the catalyst on the surface of the resin particle, for example, after adding the resin particle to a solution containing palladium chloride and tin chloride, the surface of the resin particle is activated with an acid solution or an alkali solution, and the resin particle A method of depositing palladium on the surface of and how to do it. As the reducing agent, a phosphorus-containing reducing agent is used. In addition, as the reducing agent, a metal portion containing phosphorus can be formed by using a phosphorus-containing reducing agent.

In the electroless plating process, in the electroless high-purity nickel plating method using a plating solution containing a nickel-containing compound, a complexing agent and a reducing agent, a high-purity nickel plating solution containing hydrazine as a reducing agent is suitably used.

By immersing the resin particles in the high-purity nickel plating bath, high-purity nickel plating can be deposited on the surface of the resin particles having the catalyst formed thereon, and a metal portion of high-purity nickel can be formed.

Examples of the nickel-containing compound include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate. The nickel-containing compound is preferably nickel chloride.

Examples of the reducing agent include hydrazine monohydrate, hydrazine hydrochloride and hydrazine sulfate. The reducing agent is preferably hydrazine monohydrate.

Examples of the complexing agent include monocarboxylic acid-based complexing agents such as sodium acetate and sodium propionate, dicarboxylic acid-based complexing agents such as disodium malonate, tricarboxylic acid-based complexing agents such as disodium succinate, lactic acid, DL-malic acid, and rho and hydroxy acid-based complexing agents such as cell salt, sodium citrate and sodium gluconate, amino acid-based complexing agents such as glycine and EDTA, amine-based complexing agents such as ethylenediamine, and organic acid-based complexing agents such as maleic acid. It is preferable that the said complexing agent is glycine which is an amino acid type complexing agent.

In order to form protrusions having a needle-like shape tapering toward the end on the outer surface of the metal part, the pH of the plating solution is preferably adjusted to 8.0 or higher. In the electroless plating solution using hydrazine as a reducing agent, when nickel is reduced by the oxidation reaction of hydrazine, it is accompanied by a sharp drop in pH. In order to suppress the abrupt decrease in the pH, it is preferable to use a buffering agent such as phosphoric acid, boric acid, or carbonic acid. It is preferable that the said buffering agent is boric acid which has the effect of a buffering action of pH 8.0 or more.

The ratio (average height (b)/average diameter (c)) of the average height (b) of the plurality of projections to the average diameter (c) of the bases of the plurality of projections depends on the thickness of the metal part, and can be controlled by the immersion time of The plating temperature is preferably 30°C or higher, preferably 100°C or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.

Next, an example of a method of forming a palladium-nickel alloy plating layer on the surface of a resin particle by electroless plating and a projection having a needle-like shape tapering toward the end on the outer surface of the metal part will be described.

In the said catalysis process, the catalyst used as the starting point for forming a plating layer by electroless-plating is formed in the surface of a resin particle.

As a method of forming the catalyst on the surface of the resin particle, for example, after adding the resin particle to a solution containing palladium chloride and tin chloride, the surface of the resin particle is activated with an acid solution or an alkali solution, and the resin particle A method of depositing palladium on the surface of and how to do it. As the reducing agent, a phosphorus-containing reducing agent is used. In addition, as the reducing agent, a phosphorus-containing metal portion can be formed by using a phosphorus-containing reducing agent.

In the electroless plating process, in the electroless palladium-nickel plating method using a plating solution containing a nickel-containing compound, a palladium compound, a stabilizer, a complexing agent, and a reducing agent, a palladium-nickel alloy plating solution containing hydrazine as a reducing agent is suitable is used sparingly

By immersing the resin particles in a palladium-nickel alloy plating bath, the catalyst can deposit palladium-nickel alloy plating on the surface of the resin particles formed on the surface, and a palladium-nickel metal part can be formed.

Examples of the nickel-containing compound include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate. The nickel-containing compound is preferably nickel sulfate.

Examples of the palladium-containing compound include dichloroethylenediaminepalladium(II), palladium chloride, dichlorodiamminepalladium(II), dinitrodiamminepalladium(II), tetraamminepalladium(II)nitrate, tetraamminepalladium(II)sulfate, and oxalatodiammine palladium (II), tetraammine palladium (II) oxalate, and tetraammine palladium (II) chloride. The palladium-containing compound is preferably palladium chloride.

As said stabilizer, a lead compound, a bismuth compound, a thallium compound, etc. are mentioned. Specific examples of these compounds include sulfates, carbonates, acetates, nitrates and hydrochlorides of metals (lead, bismuth, and thallium) constituting the compounds. In consideration of the effect on the environment, a bismuth compound or a thallium compound is preferred. As for these preferable stabilizers, only 1 type may be used and 2 or more types may be used together.

Examples of the reducing agent include hydrazine monohydrate, hydrazine hydrochloride and hydrazine sulfate. The reducing agent is preferably hydrazine monohydrate.

Examples of the complexing agent include monocarboxylic acid complexing agents such as sodium acetate and sodium propionate, dicarboxylic acid complexing agents such as disodium malonate, tricarboxylic acid complexing agents such as disodium succinate, lactic acid, DL-malic acid, and rho and hydroxy acid-based complexing agents such as cell salt, sodium citrate and sodium gluconate, amino acid-based complexing agents such as glycine and EDTA, amine-based complexing agents such as ethylenediamine, and organic acid-based complexing agents such as maleic acid. The complexing agent is preferably ethylenediamine, which is an amino acid-based complexing agent.

In order to form protrusions having a needle-like shape tapering toward the end on the outer surface of the metal part, it is preferable to adjust the pH of the plating solution to 8.0 to 10.0. If the pH is 7.5 or less, the stability of the plating solution is lowered and bath decomposition is caused, so it is preferable to set the pH to 8.0 or more.

The ratio (average height (b)/average diameter (c)) of the average height (b) of the plurality of projections to the average diameter (c) of the bases of the plurality of projections depends on the thickness of the metal part, and can be controlled by the immersion time of The plating temperature is preferably 30°C or higher, preferably 100°C or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.

Next, an example of a method of forming an alloy plating layer containing cobalt and nickel on the surface of a resin particle by electroless plating and a projection having a needle-like shape tapering toward the end on the outer surface of the metal part will be described.

In the said catalysis process, the catalyst used as the starting point for forming a plating layer by electroless-plating is formed in the surface of a resin particle.

As a method of forming the catalyst on the surface of the resin particle, for example, after adding the resin particle to a solution containing palladium chloride and tin chloride, the surface of the resin particle is activated with an acid solution or an alkali solution, and the resin particle A method of depositing palladium on the surface of and how to do it. As the reducing agent, a phosphorus-containing reducing agent is used. In addition, as the reducing agent, a metal portion containing phosphorus can be formed by using a phosphorus-containing reducing agent.

In the electroless plating process, in the electroless cobalt-nickel-phosphorus alloy plating method using a plating solution containing a cobalt-containing compound, an inorganic additive, a complexing agent and a reducing agent, a hypophosphorous acid compound is included as a reducing agent, and the reducing agent is reacted As the starting metal catalyst, a cobalt-nickel-phosphorus alloy plating solution containing a cobalt-containing compound is suitably used.

By immersing the resin particles in the cobalt-nickel-phosphorus alloy plating bath, the catalyst can precipitate a cobalt-nickel-phosphorus alloy on the surface of the resin particles formed on the surface, thereby forming a metal part containing cobalt, nickel and phosphorus. can

The cobalt-containing compound is preferably cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, or cobalt carbonate. The cobalt-containing compound is more preferably cobalt sulfate.

Examples of the nickel-containing compound include nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel nitrate. The nickel-containing compound is preferably nickel sulfate.

As said phosphorus containing reducing agent, hypophosphorous acid, sodium hypophosphite, etc. are mentioned. In addition to the phosphorus-containing reducing agent, a boron-containing reducing agent may be used. As said boron-containing reducing agent, dimethylamine borane, sodium borohydride, potassium borohydride, etc. are mentioned.

The complexing agent is a monocarboxylic acid complexing agent such as sodium acetate and sodium propionate, a dicarboxylic acid complexing agent such as disodium malonate, a tricarboxylic acid complexing agent such as disodium succinate, lactic acid, DL-malic acid, and Rochelle salt , a hydroxy acid-based complexing agent such as sodium citrate and sodium gluconate, an amino acid-based complexing agent such as glycine and EDTA, an amine-based complexing agent such as ethylenediamine, an organic acid-based complexing agent such as maleic acid, or a salt thereof . Only 1 type may be used for these preferable complexing agents, and 2 or more types may be used together.

The inorganic additive is preferably ammonium sulfate, ammonium chloride or boric acid. As for these preferable inorganic additives, only 1 type may be used and 2 or more types may be used together. The inorganic additive is considered to act to promote precipitation of the electroless cobalt plating layer.

In order to form protrusions having a needle-like shape tapering toward the end on the outer surface of the metal part, it is preferable to control the molar ratio of the cobalt compound and the nickel compound. The amount of the cobalt compound used is preferably 2 to 100 times the molar ratio to the nickel compound.

Moreover, even if it does not use the said inorganic additive, the processus|protrusion which has a needle-like shape is obtained. It is preferable to use an inorganic additive, and it is particularly preferable to use ammonium sulfate in order to form a protrusion having a smaller apex angle and a sharply tapering shape.

The ratio (average height (b)/average diameter (c)) of the average height (b) of the plurality of projections to the average diameter (c) of the bases of the plurality of projections depends on the thickness of the metal part, and can be controlled by the immersion time of The plating temperature is preferably 30°C or higher, preferably 100°C or lower, and the immersion time in the plating bath is preferably 5 minutes or longer.

The thickness of the entire metal portion in the non-protrusion portion is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, particularly preferably 50 nm or more, preferably 1000 nm or less, more preferably Preferably it is 800 nm or less, More preferably, it is 500 nm or less, Especially preferably, it is 400 nm or less. The thickness of the entire metal portion in the portion without the convex portion is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, particularly preferably 50 nm or more, preferably 1000 nm or less, more preferably Preferably it is 800 nm or less, More preferably, it is 500 nm or less, Especially preferably, it is 400 nm or less. If the thickness of the whole metal part is more than the said lower limit, peeling of a metal part is suppressed. The difference between a substrate particle and the coefficient of thermal expansion of a metal part becomes it small that the thickness of the whole metal part is below the said upper limit, and it becomes difficult to peel a metal part from a substrate particle. The thickness of the metal part represents the thickness of the entire metal part (the total thickness of the first and second metal parts) when the metal part has a plurality of metal parts (the first metal part and the second metal part).

When the metal part has a plurality of metal parts, the thickness of the metal part in the non-protrusion portion of the outermost layer is preferably 1 nm or more, more preferably 10 nm or more, preferably 500 nm or less, more preferably less than 100 nm. When the metal part has a plurality of metal parts, the thickness of the metal part in the portion without the convex part of the outermost layer is preferably 1 nm or more, more preferably 10 nm or more, preferably 500 nm or less, more preferably less than 100 nm. When the thickness of the metal portion of the outermost layer is equal to or greater than the lower limit and equal to or less than the upper limit, the coating by the metal portion of the outermost layer can be made uniform, the corrosion resistance is sufficiently increased, and the connection resistance between the electrodes is sufficiently lowered. Further, in the case where the outermost layer is more expensive than the metal portion of the inner layer, the lower the thickness of the outermost layer, the lower the cost.

The thickness of the metal portion can be measured, for example, by observing the cross section of the metal-containing particles using a transmission electron microscope (TEM).

[Core material]

Preferably, the metal-containing particles include a plurality of core substances that raise the surface of the metal portion, and the surface of the metal portion is raised so as to form a plurality of the convex portions or a plurality of the projections in the metal portion. It is more preferable to provide a plurality of core substances. Since the core material is embedded in the metal part, it is easy to make the metal part have a plurality of the convex parts or a plurality of protrusions on the outer surface. However, in order to form convex parts or protrusions on the outer surfaces of the metal-containing particles and the metal part, it is not necessarily necessary to use a core material. For example, as a method of forming convex parts or projections by electroless plating without using a core material, metal nuclei are generated by electroless plating to attach metal nuclei to the surface of substrate particles or metal parts, and furthermore, electroless plating The method of forming a metal part by sea plating, etc. are mentioned.

As a method of forming the said convex part or processus|protrusion, after making a core substance adhere to the surface of a substrate particle, After forming a metal part by electroless-plating in the method of forming a metal part by electroless-plating, and the surface of a substrate particle , a method of attaching a core substance and forming a metal part by electroless plating, and the like.

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

Since the core material is embedded in the metal part, it is easy to make the metal part have a plurality of the convex parts or a plurality of protrusions on the outer surface. However, in order to form convex parts or projections on the conductive surface of the metal-containing particles and the surface of the metal part, it is not necessarily necessary to use a core material.

As a method of forming the said convex part or processus|protrusion, after making a core substance adhere to the surface of a substrate particle, After forming a metal part by electroless-plating on the surface of a method of forming a metal part by electroless-plating, The method of adding a core substance in the middle stage of making a core substance adhere and forming a metal part by the method of forming a metal part by electroless-plating and electroless-plating on the surface of a substrate particle, etc. are mentioned.

Examples of the material of the core material include a conductive material and a non-conductive material. Examples of the conductive substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers. Polyacetylene etc. are mentioned as said conductive polymer. Examples of the non-conductive material include silica, alumina, barium titanate, and zirconia. Especially, since electroconductivity can be raised and connection resistance can be lowered effectively, a metal is preferable. The core material is preferably a metal particle. As a metal which is the material of the said core substance, the metal listed as a material of the said electrically-conductive material can be used suitably.

Specific examples of the material of the core material include barium titanate (Mohs hardness 4.5), nickel (Mohs hardness 5), silica (silicon dioxide, Mohs hardness 6-7), titanium oxide (Mohs hardness 7), zirconia (Mohs hardness 8) to 9), alumina (Mohs hardness 9), tungsten carbide (Mohs hardness 9), diamond (Mohs hardness 10), and the like. The inorganic particles are preferably nickel, silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond, more preferably silica, titanium oxide, zirconia, alumina, tungsten carbide or diamond, titanium oxide, zirconia, alumina, It is more preferably tungsten carbide or diamond, particularly preferably zirconia, alumina, tungsten carbide or diamond. The material Mohs hardness of the core material is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, particularly preferably 7.5 or more.

The shape of the core material is not particularly limited. It is preferable that the shape of the core material is lumpy. As a core substance, a particulate-form mass, the aggregated mass in which several microparticles aggregated, the amorphous mass, etc. are mentioned, for example.

The average diameter (average particle diameter) of the core material is preferably 0.001 µm or more, more preferably 0.05 µm or more, preferably 0.9 µm or less, and more preferably 0.2 µm or less. When the average diameter of the core material is equal to or greater than the lower limit and equal to or less than the upper limit, the connection resistance between the electrodes is effectively lowered.

The "average diameter (average particle diameter)" of the said core substance shows a number average diameter (number average particle diameter). The average diameter of a core substance is calculated|required by observing 50 arbitrary core substances with an electron microscope or an optical microscope, and calculating an average value.

[insulating material]

The metal-containing particles according to the present invention preferably include an insulating material disposed on the outer surface of the metal part. In this case, when metal-containing particles are used for connection between electrodes, short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of metal-containing particles are in contact, an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between the electrodes adjacent to each other in the horizontal direction, not between the upper and lower electrodes. In addition, by pressing the metal-containing particles with the two electrodes at the time of connection between the electrodes, the insulating substance between the metal portion of the metal-containing particles and the electrode can be easily removed. Since the metal portion has a plurality of projections on the outer surface, the insulating material between the metal portion of the metal-containing particles and the electrode can be easily removed. Further, when the metal portion has a plurality of convex portions on the outer surface, the insulating substance between the metal portion of the metal-containing particles and the electrode can be easily excluded.

It is preferable that the said insulating material is an insulating particle at the point that the said insulating material can be excluded more easily at the time of compression between electrodes.

Specific examples of the insulating resin that is the material of the insulating substance include polyolefin compounds, (meth)acrylate polymers, (meth)acrylate copolymers, block polymers, thermoplastic resins, crosslinked products of thermoplastic resins, thermosetting resins, and water-soluble resins. can

Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. As said (meth)acrylate polymer, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, etc. are mentioned. Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB-type styrene-butadiene block copolymer, SBS-type styrene-butadiene block copolymer, 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 water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and methyl cellulose. Especially, water-soluble resin is preferable and polyvinyl alcohol is more preferable.

As a method of disposing an insulating material on the surface of the metal part, a chemical method, a physical or mechanical method, or the like may be mentioned. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, an emulsion polymerization method, and the like. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic deposition, spraying, dipping, and vacuum vapor deposition. Among them, a method of disposing the insulating material through a chemical bond on the surface of the metal part is preferable because the insulating material is difficult to be detached.

The outer surface of the said metal part and the surface of an insulating substance (insulating particle etc.) may be coat|covered with the compound which has a reactive functional group, respectively. The outer surface of the metal part and the surface of the insulating substance may not be directly chemically bonded, or may be chemically bonded indirectly by a compound having a reactive functional group. After the carboxyl group is introduced into the outer surface of the metal part, the carboxyl group may be chemically bonded to the surface functional group of the insulating material through a polymer electrolyte such as polyethyleneimine.

The average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the metal-containing particles and the use of the metal-containing particles. The average diameter (average particle diameter) of the insulating material is preferably 0.005 µm or more, more preferably 0.01 µm or more, preferably 1 µm or less, and more preferably 0.5 µm or less. When the average diameter of an insulating substance is more than the said minimum and metal containing particle|grains are disperse|distributed in binder resin, it will become difficult for the metal parts in several metal containing particle|grains to contact. When the average diameter of the insulating material is equal to or less than the upper limit, there is no need to increase the pressure too high in order to exclude the insulating material between the electrode and the metal-containing particles at the time of connection between the electrodes, and there is no need to heat to a high temperature.

"Average diameter (average particle diameter)" of the said insulating substance shows a number average diameter (number average particle diameter). The average diameter of an insulating material is calculated|required using a particle size distribution measuring apparatus etc.

(Particle Linkage)

As described above, the metal-containing particles according to the present invention can form the particle connection body shown in FIG. 15 by melting and then solidifying the projections of the metal part. Such a particle-connected body is useful as a novel material that can improve connection reliability higher than that of conventional metal-containing particles. That is, the present inventors further discovered the following invention as a novel connection material.

1) A particle-connected body in which a plurality of metal-containing particles (distinct from the metal-containing particles according to the present invention, also referred to as a metal-containing particle body) are connected through columnar connecting portions comprising metal.

2) The particle connecting body of 1) above, wherein the columnar connecting portion contains a metal of the same kind as the metal contained in the metal-containing particles.

3) The particle assembly according to 1) or 2) above, wherein the metal-containing particles constituting the particle assembly are derived from the metal-containing particles according to the present invention.

4) The particle connection according to any one of 1) to 3) above, wherein the metal-containing particles and the columnar connection portion constituting the particle connection body are formed by melting and solidifying the projections of the metal-containing particles according to the present invention. sifter.

5) The particle connection body according to any one of 1) to 4) above, wherein the columnar connection part is derived from the projection of the metal-containing particle according to the present invention.

Although the particle-connected body of the present invention can be manufactured by the above-described method, the manufacturing method is not limited to the above-mentioned method. For example, the metal-containing particles and the columnar body may be separately manufactured, and the metal-containing particles may be connected by the columnar body to form the columnar connecting portion.

A columnar connection part or a polygonal columnar connection part may be sufficient as the said columnar connection part, and the center part of a pillar may thicken and may become thin.

In the columnar connection portion, the diameter (d) of the circumscribed circle of the interface with the metal-containing particles is preferably 3 nm or more, more preferably 100 nm or more, preferably 10000 nm or less, more preferably 1000 nm or less. .

In the above columnar connecting portion, the length l of the columnar connecting portion is preferably 3 nm or more, more preferably 100 nm or more, preferably 10000 nm or less, more preferably 1000 nm or less.

In the columnar connecting portion, the ratio ((d)/(l)) of the length l of the columnar connecting portion to the diameter d of the circumscribed circle of the connection surface with the metal-containing particle ((d)/(l)) is preferably 0.001 or more , More preferably, it is 0.1 or more, Preferably it is 100 or less, More preferably, it is 10 or less.

The particle combination of the present invention may be a combination of two metal-containing particles as shown in Fig. 15, or a combination of three or more metal-containing particles.

(connection material)

The connecting material which concerns on this invention is used suitably for forming the connecting part which connects two connection object members. The connecting material includes the above-mentioned metal-containing particles and a resin. The connecting material is preferably used for forming the connecting portion by melting and then solidifying the tips of the projections of the metal portion of the plurality of metal-containing particles.

The said resin is not specifically limited. The resin is a binder for dispersing the metal-containing particles. It is preferable that a thermoplastic resin or curable resin is included, and, as for the said resin, it is more preferable that curable resin is included. As said curable resin, a photocurable resin and a thermosetting resin are mentioned. The photocurable resin preferably includes a photocurable resin and a photopolymerization initiator. The thermosetting resin preferably includes a thermosetting resin and a thermosetting agent. As said resin, a vinyl resin, a thermoplastic resin, curable resin, a thermoplastic block copolymer, an elastomer etc. are mentioned, for example. As for the said resin, only 1 type may be used and 2 or more types may be used together.

As said vinyl resin, vinyl acetate resin, an acrylic resin, a styrene resin, etc. are mentioned, for example. As said thermoplastic resin, polyolefin resin, ethylene-vinyl acetate copolymer, 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. In addition, room temperature curable resin, thermosetting resin, photocurable resin, or moisture curable resin may be sufficient as the said curable resin. As the thermoplastic block copolymer, for example, a hydrogenated product of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, and hydrogen of a styrene-isoprene-styrene block copolymer Additives etc. are mentioned. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

When the projections of the metal part contain a metal oxide, a reducing agent is preferably used. Examples of the reducing agent include an alcohol compound (a compound having an alcoholic hydroxyl group), a carboxylic acid compound (a compound having a carboxyl group), and an amine compound (a compound having an amino group). As for the said reducing agent, only 1 type may be used and 2 or more types may be used together.

Alkyl alcohol is mentioned as said alcohol compound. Specific examples of the alcohol compound include ethanol, propanol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol , pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol and icosyl alcohol. In addition, as said alcohol compound, it is not limited to a primary alcohol type compound, A secondary alcohol type compound, a tertiary alcohol type compound, an alkanediol, and the alcohol compound which has a cyclic structure can also be used. Moreover, as said alcohol compound, you may use the compound which has many alcohol groups, such as ethylene glycol and triethylene glycol. Moreover, as said alcohol compound, you may use compounds, such as a citric acid, ascorbic acid, and glucose.

Alkyl carboxylic acid etc. are mentioned as said carboxylic acid compound. Specific examples of the carboxylic acid compound include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid. acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid and icosanic acid; and the like. In addition, the said carboxylic acid compound is not limited to a primary carboxylic acid type compound, A secondary carboxylic acid type compound, a tertiary carboxylic acid type compound, dicarboxylic acid, and the carboxyl compound which has a cyclic structure can also be used.

An alkylamine etc. are mentioned as said amine compound. Specific examples of the amine compound include butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, and hexadecylamine. amine, heptadecylamine, octadecylamine, nonadecylamine and icodecylamine; and the like. Moreover, the said amine compound may have a branched structure. Examples of the amine compound having a branched structure include 2-ethylhexylamine and 1,5-dimethylhexylamine. The amine compound is not limited to a primary amine compound, and a secondary amine compound, a tertiary amine compound, and an amine compound having a cyclic structure may also be used.

The reducing agent may be an organic substance having an aldehyde group, an ester group, a sulfonyl group or a ketone group, or an organic substance such as a carboxylate metal salt. While the carboxylate metal salt is used also as a precursor of metal particles, since it contains an organic substance, it is also used as a reducing agent for metal oxide particles.

In addition to the metal-containing particles and the resin, the connection material may include, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant. You may contain various additives, such as

It is preferable that the said connection material is used for a conductive connection, and it is preferable that it is a conductive connection material. It is preferable that the said connection material is used for an anisotropic conductive connection, and it is preferable that it is an anisotropic conductive connection material. The connecting material can be used as a paste, a film, or the like. When the said connection material is a film, the film which does not contain metal containing particle|grains may be laminated|stacked on the film containing metal containing particle|grains. It is preferable that it is an electrically conductive paste, and, as for the said paste, it is more preferable that it is an anisotropic electrically conductive paste. It is preferable that it is a conductive film, and, as for the said film, it is more preferable that it is an anisotropic conductive film.

In 100% by weight of the connecting material, the content of the resin is preferably 1% by weight or more, more preferably 5% by weight or more and 10% by weight or more, 30% by weight or more, or 50% by weight or more, 70 weight% or more may be sufficient, Preferably it is 99.99 weight% or less, More preferably, it is 99.9 weight% or less. Connection reliability becomes still higher that content of the said resin is more than the said minimum and below the said upper limit.

The content of the metal-containing particles in 100% by weight of the connection material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 99% by weight or less, more preferably 95% by weight or less; 80 weight% or less may be sufficient, 60 weight% or less may be sufficient, 40 weight% or less may be sufficient, 20 weight% or less may be sufficient, and 10 weight% or less may be sufficient. Connection reliability becomes still higher that content of the said metal containing particle is more than the said minimum and below the said upper limit. In addition, when the content of the metal-containing particles is equal to or greater than the lower limit and equal to or less than the upper limit, the metal-containing particles can be sufficiently present between the first and second connection object members, and the first and second connection objects due to the metal-containing particles It can further suppress that the space|interval between members narrows partially. For this reason, it can also suppress that the heat dissipation property of a connection part becomes low partially.

The said connection material may contain the metal atom containing particle|grains which do not have a substrate particle separately from metal containing particle|grains.

As said metal atom containing particle|grains, a metal particle, a metal compound particle, etc. are mentioned. The metal compound particles contain a metal atom and atoms other than the metal atom. Specific examples of the metal compound particles include metal oxide particles, metal carbonate particles, metal carboxylate particles, and metal complex particles. The metal compound particles are preferably metal oxide particles. For example, the metal oxide particles are sintered after becoming metal particles by heating at the time of connection in the presence of a reducing agent. The metal oxide particles are precursors of metal particles. As said metal carboxylate particle|grains, a metal acetate particle etc. are mentioned.

As a metal which comprises the said metal particle and the said metal oxide particle, silver, copper, nickel, gold|metal|money, etc. are mentioned. Silver or copper is preferred, and silver is particularly preferred. Accordingly, the metal particles are preferably silver particles or copper particles, and more preferably silver particles. The metal oxide particles are preferably silver oxide particles or copper oxide particles, and more preferably silver oxide particles. When silver particle and silver oxide particle are used, there are few residues after connection, and the volume reduction rate is also very small. _{Ag 2} O and AgO are mentioned as silver oxide in this silver oxide particle.

The metal atom-containing particles are preferably sintered by heating at less than 400°C. The temperature at which the metal atom-containing particles are sintered (sintering temperature) is more preferably 350°C or lower, preferably 300°C or higher. When the temperature at which the metal atom-containing particles are sintered is equal to or less than the upper limit or less than the upper limit, sintering can be performed efficiently, the energy required for sintering can be reduced, and the environmental load can be reduced.

The connection material containing particles containing metal atoms is a connection material containing metal particles having an average particle diameter of 1 nm or more and 100 nm or less, or a connection material containing metal oxide particles having an average particle diameter of 1 nm or more and 50 μm or less and a reducing agent. it is preferable When such a connecting material is used, it is possible to favorably sinter the metal atom-containing particles by heating at the time of connecting. The average particle diameter of the metal oxide particles is preferably 5 µm or less. The particle diameter of the metal atom-containing particles indicates the diameter when the metal atom-containing particles are spherical, and indicates the maximum diameter when the metal atom-containing particles are not spherical.

The content of the metal atom-containing particles in 100% by weight of the connection material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and 100% by weight or less, preferably is 99% by weight or less, more preferably 90% by weight or less. The whole amount of the said connection material may be the said metal atom containing particle|grains. When content of the said metal atom containing particle|grains is more than the said minimum, the said metal atom containing particle|grains can be made to sinter more densely. As a result, the heat dissipation property and heat resistance in a connection part also become high.

When the metal atom-containing particles are metal oxide particles, a reducing agent is preferably used. Examples of the reducing agent include an alcohol compound (a compound having an alcoholic hydroxyl group), a carboxylic acid compound (a compound having a carboxyl group), and an amine compound (a compound having an amino group). As for the said reducing agent, only 1 type may be used and 2 or more types may be used together.

Alkyl alcohol is mentioned as said alcohol compound. Specific examples of the alcohol compound include ethanol, propanol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol , pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol and icosyl alcohol. In addition, as said alcohol compound, it is not limited to a primary alcohol type compound, A secondary alcohol type compound, a tertiary alcohol type compound, an alkanediol, and the alcohol compound which has a cyclic structure can also be used. Moreover, as said alcohol compound, you may use the compound which has many alcohol groups, such as ethylene glycol and triethylene glycol. Moreover, as said alcohol compound, you may use compounds, such as a citric acid, ascorbic acid, and glucose.

Alkyl carboxylic acid etc. are mentioned as said carboxylic acid compound. Specific examples of the carboxylic acid compound include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid. acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid and icosanic acid; and the like. In addition, the said carboxylic acid compound is not limited to a primary carboxylic acid type compound, A secondary carboxylic acid type compound, a tertiary carboxylic acid type compound, dicarboxylic acid, and the carboxyl compound which has a cyclic structure can also be used.

An alkylamine etc. are mentioned as said amine compound. Specific examples of the amine compound include butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, and hexadecylamine. amine, heptadecylamine, octadecylamine, nonadecylamine and icodecylamine; and the like. Moreover, the said amine compound may have a branched structure. Examples of the amine compound having a branched structure include 2-ethylhexylamine and 1,5-dimethylhexylamine. The amine compound is not limited to a primary amine compound, and a secondary amine compound, a tertiary amine compound, and an amine compound having a cyclic structure may also be used.

The reducing agent may be an organic substance having an aldehyde group, an ester group, a sulfonyl group, a ketone group, or the like, or an organic substance such as a carboxylate metal salt. While the carboxylate metal salt is used also as a precursor of metal particles, since it contains an organic substance, it is also used as a reducing agent for metal oxide particles.

If a reducing agent having a melting point lower than the sintering temperature (junction temperature) of the metal atom-containing particles is used, aggregation occurs at the time of bonding and voids tend to occur in the bonding portion. By use of a carboxylate metal salt, since this carboxylate metal salt does not melt|dissolve by the heating at the time of bonding, it can suppress that a void is generated. Moreover, you may use the metal compound containing an organic substance other than a carboxylate metal salt as a reducing agent.

When the reducing agent is used, the content of the reducing agent in 100% by weight of the connecting material is preferably 1% by weight or more, more preferably 10% by weight or more, preferably 90% by weight or less, more preferably is 70% by weight or less, more preferably 50% by weight or less. When content of the said reducing agent is more than the said minimum, the said metal atom containing particle|grains can be sintered more densely. As a result, the heat dissipation property and heat resistance in a joint part also become high.

The content of the metal oxide particles in 100% by weight of the connection material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 60% by weight or more, preferably 99.99% by weight or less; More preferably, it is 99.9 weight% or less, More preferably, it is 99.5 weight% or less, More preferably, it is 99 weight% or less, Especially preferably, it is 90 weight% or less, Most preferably, it is 80 weight% or less.

When the connection material is a paste, the binder used in the paste is not particularly limited. The binder is preferably lost when the metal atom-containing particles are sintered. As for the said binder, only 1 type may be used and 2 or more types may be used together.

Specific examples of the binder include aliphatic solvents, ketone solvents, aromatic solvents, ester solvents, ether solvents, alcohol solvents, paraffin solvents and petroleum solvents as solvents.

Examples of the aliphatic solvent include cyclohexane, methylcyclohexane and ethylcyclohexane. Acetone, methyl ethyl ketone, etc. are mentioned as said ketone solvent. Toluene, xylene, etc. are mentioned as said aromatic solvent. As said ester solvent, ethyl acetate, butyl acetate, isopropyl acetate, etc. are mentioned. Examples of the ether solvent include tetrahydrofuran (THF) and dioxane. Ethanol, butanol, etc. are mentioned as said alcohol solvent. Paraffinic oil, a naphthenic oil, etc. are mentioned as said paraffinic solvent. As said petroleum solvent, mineral terpene, naphtha, etc. are mentioned.

(connection structure)

The connection structure which concerns on this invention is equipped with the 1st connection object member, the 2nd connection object member, and the connection part which is connecting the 1st, 2nd connection object member. In the bonded structure which concerns on this invention, the said connection part is formed of the said metal containing particle|grains or the said connection material. The material of the connecting portion is the metal-containing particle or the connecting material.

A method for manufacturing a bonded structure according to the present invention comprises the steps of disposing the metal-containing particles or disposing the connection material between a first connection object member and a second connection object member, and heating the metal-containing particles, , a step of melting the tip of the projection of the metal part and solidifying it after melting to form a connection part connecting the first connection object member and the second connection object member with the metal-containing particles or the connection material to provide

9 is a cross-sectional view schematically showing a bonded structure using metal-containing particles according to the first embodiment of the present invention.

The connection structure 51 shown in FIG. 9 is the connection part 54 which connects the 1st connection object member 52, the 2nd connection object member 53, and the 1st, 2nd connection object members 52 and 53. ) is provided. The connecting portion 54 includes the metal-containing particles 1 and a resin (cured resin, etc.). The connecting portion 54 is formed of a connecting material containing the metal-containing particles 1 . The material of the connecting portion 54 is the above connecting material. It is preferable that the connection part 54 is formed by hardening a connection material. In addition, in FIG. 9, the front-end|tip of the projection 3a of the metal part 3 of the metal containing particle|grain 1 is solidified after melting. In the connection part 54, the joined body of the several metal containing particle|grains 1 is included. In the bonded structure 51 , the metal-containing particle 1 and the first connection object member 51 are joined, and the metal-containing particle 1 and the second connection object member 53 are joined.

Instead of the metal-containing particles 1, other metal-containing particles such as metal-containing particles 1A, 1B, 1C, 1D, 1E, 1F, and 1G may be used.

The 1st connection object member 52 has the some 1st electrode 52a on the surface (upper surface). The 2nd connection object member 53 has the some 2nd electrode 53a on the surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected by one or a plurality of metal-containing particles 1 . Therefore, the 1st, 2nd connection object members 52 and 53 are electrically connected by the metal containing particle|grains 1 . In the bonded structure 51 , the metal-containing particles 1 and the first electrode 52a are joined, and the metal-containing particles 1 and the second electrode 53a are joined.

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 connection material between a 1st connection object member and a 2nd connection object member and obtaining a laminated body, the method of heating and pressurizing this laminated body, etc. are mentioned. The pressing pressure is about 9.8×10 ⁴ to 4.9×10 ⁶ Pa. The heating temperature is about 120 to 220 °C.

Specific examples of the member to be connected include electronic components such as semiconductor chips, capacitors and diodes, and electronic components that are circuit boards such as printed circuit boards, flexible printed circuit boards, glass epoxy substrates, and glass substrates. It is preferable that the said connection object member is an electronic component. The metal-containing particles are preferably used for electrical connection of electrodes in electronic components.

Metal electrodes, such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a SUS electrode, a molybdenum electrode, and a tungsten electrode, are mentioned as an electrode provided in the said connection object member. 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 the metal oxide layer may be sufficient. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Sn, Al, Ga, etc. are mentioned as said trivalent metal element.

It is sectional drawing which shows typically the modified example of the bonded structure using the metal-containing particle|grains which concern on 1st Embodiment of this invention.

The connection structure 61 shown in FIG. 10 is the 1st connection object member 62, the 2nd connection object members 63 and 64, the 1st connection object member 62, and the 2nd connection object members 63 and 64 ) and connecting portions 65 and 66 for connecting them. The connecting portions 65 and 66 are formed using a connecting material including the metal-containing particles 1 and the other metal-containing particles 67 . The material of the connecting portions 65 and 66 is the above connecting material.

The connection part 65 and the 2nd connection object member 63 are arrange|positioned on the 1st surface (one surface) side of the 1st connection object member 62. As shown in FIG. The connection part 65 is connecting the 1st connection object member 62 and the 2nd connection object member 63. As shown in FIG.

The connection part 66 and the 2nd connection object member 64 are arrange|positioned on the 2nd surface (the other surface) side opposite to the 1st surface of the 1st connection object member 62. As shown in FIG. The connection part 66 is connecting the 1st connection object member 62 and the 2nd connection object member 64. As shown in FIG.

Between the 1st connection object member 62 and the 2nd connection object members 63 and 64, the metal containing particle|grains 1 and the metal containing particle|grains 67 are arrange|positioned, respectively. In the present embodiment, in the connecting portions 65 and 66 , the metal atom-containing particles and the metal-containing particles 1 are in a sintered state. The metal-containing particles 1 are disposed between the first to-be-connected member 62 and the second to-be-connected members 63 and 64 . The first connection object member 62 and the second connection object members 63 and 64 are connected by the metal-containing particles 1 .

The heat sink 68 is arrange|positioned on the surface opposite to the connection part 65 side of the 2nd connection object member 63. As shown in FIG. The heat sink 69 is arrange|positioned on the surface of the 2nd connection object member 64 opposite to the connection part 66 side. Therefore, the connection structure 61 is the heat sink 68, the 2nd connection object member 63, the connection part 65, the 1st connection object member 62, the connection part 66, the 2nd connection object member 64 and a portion where the heat sink 69 is stacked in this order.

As the first connection target member 62, a power semiconductor element made of Si, SiC, GaN, etc. used for a rectifier diode, a power transistor (power MOSFET, insulated gate bipolar transistor), a thyristor, a gate turn-off thyristor, a triac, etc. can be heard In the connection structure 61 provided with such a 1st connection object member 62, at the time of use of the connection structure 61, large calorie|heat amount is easy to generate|occur|produce in the 1st connection object member 62. As shown in FIG. Therefore, it is necessary to efficiently dissipate the amount of heat generated from the first connection object member 62 to the heat sinks 68 and 69 or the like. For this reason, high heat dissipation property and high reliability are calculated|required by the connection parts 65 and 66 arrange|positioned between the 1st connection object member 62 and the heat sinks 68 and 69.

Examples of the second connection target members 63 and 64 include substrates made of ceramic, plastic, or the like.

The connecting portions 65 and 66 are formed by heating the connecting material to melt the tips of the metal-containing particles and then solidifying them.

(Members for continuity inspection or members for continuity)

It is also possible to apply the particle|grain connection body and connection material of this invention to the member for conduction|electrical_connection test|inspection or the member for conduction|electrical_connection. Hereinafter, one form of the member for conduction inspection is described. In addition, the member for conduction|electrical_connection test|inspection is not limited to the following form. A sheet-like member for conduction may be sufficient as the said member for conduction|electrical_connection inspection and the said member for conduction|electrical_connection.

19A and 19B are a plan view and a cross-sectional view showing an example of a member for conduction inspection. Fig. 19(b) is a cross-sectional view taken along line A-A in Fig. 19(a).

The member 11 for conduction inspection shown in FIGS. 19A and 19B includes a base 12 having a through hole 12a, and a conductive part ( 13) is provided. The material of the conductive portion 13 includes the metal-containing particles. The member 11 for conduction|electrical_connection test|inspection may be a member for conduction|electrical_connection.

The said base|substrate is a member used as the board|substrate of the said member for conduction|electrical_connection test|inspection. It is preferable that the said base|substrate has insulating property, and it is preferable that the said base|substrate is formed of an insulating material. As an insulating material, insulating resin is mentioned, for example.

Any of a thermoplastic resin and a thermosetting resin may be sufficient as the insulating resin which comprises the said base|substrate, for example. Examples of the thermoplastic resin include a polyester resin, a polystyrene resin, a polyethylene resin, a polyamide resin, an ABS resin, and a polycarbonate resin. Examples of the thermosetting resin include an epoxy resin, a urethane resin, a polyimide resin, a polyether ether ketone resin, a polyamide imide resin, a polyether imide resin, a silicone resin, and a phenol resin. As a silicone resin, a silicone rubber etc. are mentioned.

When the said base|substrate is formed of insulating resin, only 1 type may be used for the insulating resin which comprises the said base|substrate, and 2 or more types may be used together.

The substrate is, for example, in the form of a plate, a sheet, or the like. The sheet form includes a film form. The thickness of the said base|substrate can be set suitably according to the kind of member for conduction|electrical_connection test|inspection, For example, the thickness of 0.005 mm or more and 50 mm or less may be sufficient. The size of the base body in plan view can also be appropriately set according to the target inspection apparatus.

The base can be obtained, for example, by molding into a desired shape using an insulating material such as the insulating resin as a raw material.

A plurality of the through-holes of the base are disposed in the base. It is preferable that the said through-hole penetrates in the thickness direction of the said base|substrate.

Although the said through-hole of the said base|substrate may be formed in the shape of a cylinder, it is not limited to a cylinder shape, You may form in other shapes, for example, a polygonal pillar shape. In addition, the said through-hole may be formed in the tapered shape which tapers toward the end in one direction, and may be formed in the distorted shape other than that.

The size of the through-hole, for example, the apparent area of the through-hole in a plan view, can also be formed to an appropriate size, for example, it may be formed to a size that can accommodate and hold the conductive part. . If the through hole is, for example, cylindrical, the diameter of the through hole is preferably 0.01 mm or more, preferably 10 mm or less.

In addition, all of the said through-holes of the said base|substrate may be the same shape and the same size, and the shape or size of a part of the said through-holes of the said base|substrate may differ from other through-holes.

The number of the through-holes of the base body can also be set within an appropriate range, and the number of the through-holes can be set enough to allow conduction inspection, and can be appropriately set according to the target inspection apparatus. Moreover, the arrangement position of the said through-hole of the said base|substrate can also be set suitably according to the inspection apparatus made into the objective.

The method for forming the through-hole of the substrate is not particularly limited, and it is possible to form the through-hole by a known method (eg, laser processing).

The conductive portion in the through hole of the substrate has conductivity.

Specifically, the conductive part includes particles derived from the metal-containing particles. For example, the conductive portion is formed by accommodating a plurality of metal-containing particles in a through hole. The conductive portion includes an aggregate (particle group) of particles derived from metal-containing particles.

The material of the said electroconductive part may contain materials other than the said metal containing particle|grains. For example, the material of the conductive part may include a binder in addition to the metal-containing particles. When the material of the conductive portion contains a binder, the metal-containing particles are more firmly aggregated, whereby particles derived from the metal-containing particles are easily retained in the through holes.

It does not specifically limit as said binder, For example, a photocurable resin and a thermosetting resin are mentioned. The photocurable resin preferably includes a photocurable resin and a photopolymerization initiator. The thermosetting resin preferably includes a thermosetting resin and a thermosetting agent. As said resin, a silicone type copolymer, a vinyl resin, a thermoplastic resin, curable resin, a thermoplastic block copolymer, an elastomer etc. are mentioned, for example. As for the said resin, only 1 type may be used and 2 or more types may be used together.

It is preferable that the particle|grains derived from the said metal-containing particle|grains are densely filled in the said through hole, and in this case, a more reliable conduction|electrical_connection test can be performed according to the said member for conduction|electrical_connection test|inspection. It is preferable that the said electrically-conductive part is accommodated in the said through hole so that conduction|electrical_connection is possible across the front and back of the member for conduction|electrical_connection test|inspection or the member for conduction|electrical_connection.

In the said conductive part, it is preferable that the particle|grains derived from the said metal-containing particle|grains exist continuously from the surface to the back surface of the conductive part while the particle|grains derived from the said metal-containing particle are in contact with each other. In this case, the conductivity of the conductive portion is improved.

The method of accommodating the said electrically-conductive part in the said through hole is not specifically limited. For example, the conductive part can be formed in the through hole by filling the metal-containing particles into the through-holes by coating a substrate with a material containing the metal-containing particles and a binder, and curing the metal-containing particles under suitable conditions. Thereby, the conductive part is accommodated in the through hole. A solvent may be contained in the material containing the said metal-containing particle|grains and a binder as needed.

In the material containing the metal-containing particles and the binder, the content of the binder is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, in terms of solid content, with respect to 100 parts by weight of the metal-containing particles, preferably It is 70 weight part or less, More preferably, it is 50 weight part or less.

The member for conduction inspection can be used as a probe card. In addition, the said member for conduction|electrical_connection test|inspection may be provided with other components as long as the effect of this invention is not impaired.

20A to 20C are diagrams schematically showing a state in which the electrical characteristics of an electronic circuit device are inspected by a member for conduction inspection.

20A to 20C, the electronic circuit device is a BGA substrate 31 (a ball grid array substrate). The BGA substrate 31 is a substrate having a structure in which connection pads are arranged on the multilayer substrate 31A in a lattice shape, and solder balls 31B are arranged on each pad. In addition, in (a)-(c) of FIG. 20, the member 21 for conduction|electrical_connection test|inspection is a probe card. As for the member 21 for conduction|electrical_connection test|inspection, the some through-hole 22a is formed in the base|substrate 22, and the electroconductive part 23 is accommodated in the through-hole 22a. As shown in Fig. 20(a), the BGA substrate 31 and the member 21 for the conduction inspection are prepared, and as shown in Fig. 20(b), the BGA substrate 31 is brought into contact with the member 21 for the conduction inspection. and compress it. At this time, the solder ball 31B comes into contact with the conductive portion 23 in the through hole 22a. In this state, as shown in FIG. 20C , the ammeter 32 is connected to conduct a continuity test, and it is possible to determine whether the BGA substrate 31 has passed or not.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

(Example 1)

As the substrate particle A, a particle diameter prepared the divinylbenzene copolymer resin particle ("Micropearl SP-203" made by Sekisui Chemical Co., Ltd.) which is 3.0 micrometers.

After disperse|distributing 10 weight part of substrate particles A to 100 weight part of alkali solutions containing 5 weight% of palladium catalyst liquids using the ultrasonic disperser, the substrate particle A was taken out by filtering a solution. Then, the substrate particle A was added to 100 weight part of dimethylamine borane 1 weight% solution, and the surface of the substrate particle A was activated. Suspension (A) was obtained by adding and disperse|distributing the substrate particle A by which the surface was activated sufficiently by adding and disperse|distributing to 500 weight part of distilled water, after washing with water.

Then, 1 part by weight of a metallic nickel particle slurry (“2020SUS” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter of 150 nm) is added to the suspension (A) over 3 minutes, and the suspension (B) containing the substrate particles A to which the core substance adheres. ) was obtained.

The suspension (B) was put in the solution containing 20 g/L of copper sulfate and 30 g/L of ethylenediamine tetraacetic acid, and the particle|grain liquid mixture (C) was obtained.

In addition, as an electroless copper plating solution, a copper plating solution obtained by adjusting pH 10.5 with ammonia to a mixed solution containing 250 g/L of copper sulfate, 150 g/L of ethylenediaminetetraacetic acid, 100 g/L of sodium gluconate and 50 g/L of formaldehyde (D ) was prepared.

In addition, as an electroless silver plating solution, a silver plating solution (E) in which a mixed solution containing 30 g/L of silver nitrate, 100 g/L of succinimide, and 20 g/L of formaldehyde was adjusted to pH 8.0 with aqueous ammonia was prepared.

In addition, a plating solution (F) (pH 10.0) for forming protrusions containing 100 g/L of dimethylamine borane and 0.5 g/L of sodium hydroxide was prepared.

The said copper plating liquid (D) was dripped gradually to the particle|grain liquid mixture (C) in a dispersed state adjusted to 55 degreeC, and electroless copper plating was performed. The dripping rate of the copper plating solution (D) was 30 mL/min, and the dripping time was 30 minutes, and electroless copper plating was performed. In this way, the copper metal part is arrange|positioned on the surface of the resin particle, and the particle|grain liquid mixture (G) containing the particle|grains provided with the metal part which has a convex part on the surface was obtained.

Then, the copper metal part is arrange|positioned on the surface of the said substrate particle A by taking out particle|grains by filtering the particle|grain liquid mixture (G), and washing with water, and the particle|grain provided with the metal part which has a convex part in the surface was obtained. After sufficiently washing this particle with water, it added and disperse|distributed to 500 weight part of distilled water, the particle|grain liquid mixture (H) was obtained.

Next, the said silver plating liquid (E) was dripped gradually to the particle|grain liquid mixture (H) of the dispersed state adjusted to 60 degreeC, and electroless silver plating was performed. The dropping rate of the silver plating solution (E) was 10 mL/min, and the dropping time was 30 minutes, and electroless silver plating was performed. Then, the said plating liquid (F) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (F) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During dripping of the plating liquid (F) for projection formation, silver plating was performed, disperse|distributing the generated silver projection nuclei with ultrasonic stirring (projection|protrusion formation process). Then, copper and silver metal part (thickness of the whole metal part in a part without a convex part: 0.1 micrometer) is arrange|positioned on the surface of substrate particle A by taking out particle|grains by filtration, washing with water, and drying, the surface It has a convex part, and the metal containing particle|grains provided with the metal part which has a some processus|protrusion on the surface of a convex part were obtained.

(Example 2)

Except having changed the metallic nickel particle slurry into the alumina particle slurry (average particle diameter of 150 nm), it carried out similarly to Example 1, and obtained the metal containing particle|grains.

(Example 3)

The suspension (A) obtained in Example 1 was put into a solution containing 40 ppm of nickel sulfate, 2 g/L of trisodium citrate, and 10 g/L of aqueous ammonia to obtain a particle mixture (B).

As a plating solution for needle formation, copper sulfate 100g/L, nickel sulfate 10g/L, sodium hypophosphite 100g/L, trisodium citrate 70g/L, boric acid 10g/L, and polyethylene glycol 1000 (molecular weight: 1000) as a nonionic surfactant A plating solution (C) for forming needles, which is an electroless copper-nickel-phosphorus alloy plating solution in which a mixed solution containing 5 mg/L was adjusted to pH 10.0 with aqueous ammonia, was prepared.

In addition, as an electroless silver plating solution, a silver plating solution (D) in which a mixed solution of 30 g/L silver nitrate, 100 g/L succinimide, and 20 g/L formaldehyde was adjusted to pH 8.0 with aqueous ammonia was prepared.

In addition, a plating solution (E) (pH 10.0) for forming protrusions containing 100 g/L of dimethylamine borane and 0.5 g/L of sodium hydroxide was prepared.

The plating solution for forming needles (C) was gradually added dropwise to the particle mixture (B) in a dispersed state adjusted to 70°C to form needles. Electroless copper-nickel-phosphorus alloy plating was performed (acicular projection formation and copper-nickel-phosphorus alloy plating process) at a dropping rate of the plating solution (C) for forming needles at 40 mL/min and a dropping time of 60 minutes. Then, by filtering, particle|grains were taken out, the copper- nickel- phosphorus alloy metal part is arrange|positioned on the surface of the substrate particle A, and the particle|grain (F) provided with the metal part which has a convex part in the surface was obtained. A suspension (G) was obtained by adding and dispersing the particles (F) to 500 parts by weight of distilled water.

Then, by filtering suspension (G), particle|grains were taken out, and the copper- nickel- phosphorus alloy metal part is arrange|positioned on the surface of the said substrate particle A by washing with water, and the particle|grain provided with the metal part which has needle-shaped convex parts on the surface was obtained. . After sufficiently washing this particle with water, it added and disperse|distributed to 500 weight part of distilled water, the particle|grain liquid mixture (H) was obtained.

Then, the said silver plating liquid (D) was dripped gradually to the particle|grain liquid mixture (H) of the dispersed state adjusted to 60 degreeC, and electroless silver plating was performed. The dropping rate of the silver plating solution (D) was 10 mL/min, and the dropping time was 30 minutes, and electroless silver plating was performed. Then, the said plating liquid (E) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (E) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During dripping of the plating liquid (E) for projection formation, silver plating was performed, disperse|distributing the generated silver projection nuclei with ultrasonic stirring (projection|protrusion formation process). Then, the copper- nickel- phosphorus alloy and silver metal part (thickness of the whole metal part in a part without a convex part: 0.1 micrometer) on the surface of substrate particle A by taking out particle|grains by filtration, washing with water, and drying It arrange|positioned, it had several needle-shaped convex part on the surface, and obtained the metal containing particle|grains provided with the metal part which has a several processus|protrusion on the surface of a convex part.

(Example 4)

The suspension (A) obtained in Example 1 was put into a solution containing 80 g/L of nickel sulfate, 10 ppm of thallium nitrate, and 5 ppm of bismuth nitrate to obtain a particle mixture (B).

As a plating solution for forming needles, a mixture containing 100 g/L of nickel chloride, 100 g/L of hydrazine monohydrate, 50 g/L of trisodium citrate, and 20 mg/L of polyethylene glycol 1000 (molecular weight: 1000) was adjusted to pH 9.0 with sodium hydroxide. A plating solution (C) for forming needles, which is the adjusted electroless high-purity nickel plating solution, was prepared.

In addition, as an electroless silver plating solution, a silver plating solution (D) in which a mixed solution containing 30 g/L of silver nitrate, 100 g/L of succinimide, and 20 g/L of formaldehyde was adjusted to pH 8.0 with aqueous ammonia was prepared.

In addition, a plating solution (E) (pH 10.0) for forming protrusions containing 100 g/L of dimethylamine borane and 0.5 g/L of sodium hydroxide was prepared.

The plating solution for forming needles (C) was gradually added dropwise to the particle mixture (B) in a dispersed state adjusted to 60°C to form needles. Electroless high-purity nickel plating was performed (acicular projection formation and copper-nickel-phosphorus alloy plating process) at a dropping rate of 20 mL/min and a dropping time of 50 minutes of the plating solution (C) for forming needles. Then, the particle|grains were taken out by filtration, the high-purity nickel metal part is arrange|positioned on the surface of the substrate particle A, and the particle|grain (F) provided with the metal part which has a convex part in the surface was obtained. A suspension (G) was obtained by adding and dispersing the particles (F) to 500 parts by weight of distilled water.

Then, a high-purity nickel metal part was arrange|positioned on the surface of the said substrate particle A by taking out particle|grains by filtering suspension (G), and washing with water, and the particle|grain provided with the metal part which has needle-shaped convex part on the surface was obtained. After sufficiently washing this particle with water, it added and disperse|distributed to 500 weight part of distilled water, the particle|grain liquid mixture (H) was obtained.

Then, the said silver plating liquid (D) was dripped gradually to the particle|grain liquid mixture (H) of the dispersed state adjusted to 60 degreeC, and electroless silver plating was performed. The dropping rate of the silver plating solution (D) was 10 mL/min, and the dropping time was 30 minutes, and electroless silver plating was performed. Then, the said plating liquid (E) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (E) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During dripping of the plating liquid (E) for projection formation, silver plating was performed, disperse|distributing the generated silver projection nuclei with ultrasonic stirring (projection|protrusion formation process). Then, particle|grains are taken out by filtration, high-purity nickel and a silver metal part are arrange|positioned on the surface of the substrate particle A, It has needle-shaped convex part on the surface, The particle|grain liquid mixture provided with the metal part which has a some processus|protrusion on the surface of a convex part. (I) was obtained.

Then, high-purity nickel and silver metal part (thickness of the whole metal part in a part without a convex part: 0.1 micrometer on the surface of substrate particle A by taking out particle|grains by filtering particle liquid mixture (I), washing with water, and drying) ) is disposed, has a plurality of acicular convex portions on the surface, and metal-containing particles having a metal portion having a plurality of projections on the surface of the convex portions were obtained.

(Example 5)

The suspension (A) obtained in Example 1 was put into a solution containing 500 ppm silver nitrate, 10 g/L succinimide, and 10 g/L aqueous ammonia to obtain a particle mixture (B).

As the electroless silver plating solution, a silver plating solution (C) in which a mixed solution containing 30 g/L of silver nitrate, 100 g/L of succinimide, and 20 g/L of formaldehyde was adjusted to pH 8 with aqueous ammonia was prepared.

In addition, a plating solution (D) (pH 10.0) for forming protrusions containing 100 g/L of dimethylamine borane and 0.5 g/L of sodium hydroxide was prepared.

The said electroless silver plating liquid (C) was dripped gradually to the particle|grain liquid mixture (B) in a dispersed state adjusted to 60 degreeC, and needle-like projections were formed. The dropping rate of the electroless silver plating liquid (C) was 10 mL/min, and the dripping time was 30 minutes, and electroless silver plating was performed (silver plating process). Then, the said plating liquid (D) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (D) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During the dripping of the plating liquid (D) for projection formation, silver plating was performed, disperse|distributing the generated silver projection nuclei with ultrasonic stirring (projection|protrusion formation process). Then, a silver metal part (thickness of the whole metal part in a part without processus|protrusion: 0.1 micrometer) is arrange|positioned on the surface of substrate particle A by taking out particle|grains by filtration, washing with water, and drying, on the surface The metal-containing particle|grains provided with the metal part which has a some processus|protrusion were obtained.

(Example 6)

The suspension (A) obtained in Example 1 was put into a solution containing 500 ppm of silver potassium cyanide, 10 g/L of potassium cyanide, and 10 g/L of potassium hydroxide to obtain a particle mixture (B).

As a plating solution for needle formation, a mixed solution containing 80 g/L of silver potassium cyanide, 10 g/L of potassium cyanide, 20 mg/L of polyethylene glycol 1000 (molecular weight: 1000), 50 ppm of thiourea and 100 g/L of hydrazine monohydrate is used as potassium hydroxide A silver plating solution (C) adjusted to pH 7.5 was prepared.

The electroless silver plating solution (C) was gradually added dropwise to the particle mixture solution (B) in a dispersed state adjusted to 80°C to form needle-like projections. The dropping rate of the electroless silver plating solution (C) was 10 mL/min, and the dripping time was 60 minutes, and electroless silver plating was performed (acicular processus|protrusion formation and silver plating process). Thereafter, the particles are taken out by filtration, washed with water, and dried to arrange a silver metal part (the total thickness of the metal part in the non-protrusion part: 0.1 µm) on the surface of the resin particle, and a plurality of needles are formed on the surface. The metal-containing particle|grains provided with the silver metal part in which the processus|protrusion was formed were obtained.

(Example 7)

The suspension (A) obtained in Example 1 was put into a solution containing 500 ppm of silver potassium cyanide, 10 g/L of potassium cyanide, and 10 g/L of potassium hydroxide to obtain a particle mixture (B).

As a plating solution for needle formation, a mixed solution containing 80 g/L of silver potassium cyanide, 10 g/L of potassium cyanide, 20 mg/L of polyethylene glycol 1000 (molecular weight: 1000), 50 ppm of thiourea and 100 g/L of hydrazine monohydrate is used as potassium hydroxide A silver plating solution (C) adjusted to pH 7.5 was prepared.

In addition, as an electroless silver plating solution, a silver plating solution (D) in which a mixed solution containing 30 g/L of silver nitrate, 100 g/L of succinimide, and 20 g/L of formaldehyde was adjusted to pH 8.0 with aqueous ammonia was prepared.

In addition, a plating solution (E) (pH 10.0) for forming protrusions containing 100 g/L of dimethylamine borane and 0.5 g/L of sodium hydroxide was prepared.

The electroless silver plating solution (C) was gradually added dropwise to the particle mixture solution (B) in a dispersed state adjusted to 80°C to form needle-like projections. The dropping rate of the electroless silver plating liquid (C) was 10 mL/min, and the dripping time was 45 minutes, and electroless silver plating was performed (acicular processus|protrusion formation and silver plating process).

Then, by filtering, particle|grains were taken out, the silver metal part is arrange|positioned on the surface of the substrate particle A, and the particle|grain (F) provided with the metal part which has a needle-shaped convex part in the surface was obtained. A particle mixture (G) was obtained by adding and dispersing the particles (F) to 500 parts by weight of distilled water.

Next, the said silver plating liquid (D) was dripped gradually to the particle|grain liquid mixture (G) in a dispersed state adjusted to 60 degreeC, and electroless silver plating was performed. The dropping rate of the silver plating solution (D) was 10 mL/min, and the dropping time was 30 minutes, and electroless silver plating was performed. Then, the said plating liquid (E) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (E) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During dripping of the plating liquid (E) for projection formation, silver plating was performed, disperse|distributing the generated silver projection nuclei with ultrasonic stirring (projection|protrusion formation process). Then, a silver metal part (thickness of the whole metal part in a part without a convex part: 0.1 micrometer) is arrange|positioned on the surface of the substrate particle A by taking out particle|grains by filtration, washing with water, and drying, and plural on the surface A metal-containing particle having a acicular convex portion and a metal portion having a plurality of projections on the surface of the convex portion was obtained.

(Example 8)

The suspension (B) obtained in Example 1 was put into a solution containing 50 g/L of nickel sulfate, 30 ppm of thallium nitrate, and 20 ppm of bismuth nitrate to obtain a particle mixture (C).

As an electroless nickel-tungsten-boron alloy plating solution, a mixed solution containing 100 g/L of nickel sulfate, 5 g/L of sodium tungstate, 30 g/L of dimethylamine borane, 10 ppm of bismuth nitrate and 30 g/L of trisodium citrate is used with sodium hydroxide. An electroless nickel-tungsten-boron alloy plating solution (D) adjusted to pH 6 was prepared.

In addition, as an electroless silver plating solution, a silver plating solution (E) in which a mixed solution of 30 g/L silver nitrate, 100 g/L succinimide, and 20 g/L formaldehyde was adjusted to pH 8.0 with aqueous ammonia was prepared.

In addition, a plating solution (F) (pH 10.0) for forming protrusions containing 100 g/L of dimethylamine borane and 0.5 g/L of sodium hydroxide was prepared.

The electroless nickel-tungsten-boron alloy plating solution (D) was gradually added dropwise to the particle mixture solution (C) in a dispersed state adjusted to 60°C to perform electroless nickel-tungsten-boron alloy plating. The electroless nickel-tungsten-boron alloy plating solution (D) was subjected to electroless nickel-tungsten-boron alloy plating at a dropping rate of 15 mL/min and a dropping time of 60 minutes. In this way, the nickel- tungsten- boron alloy metal part is arrange|positioned on the surface of the substrate particle A, and the particle|grain liquid mixture (G) containing the particle|grain provided with the metal part which has a convex part in the surface was obtained.

Then, the particle|grains were taken out by filtering the particle|grain liquid mixture (G), and the nickel- tungsten- boron alloy metal layer is arrange|positioned on the surface of the said substrate particle A by washing with water, The particle|grains provided with the metal part which has a convex part on the surface were obtained. . After sufficiently washing this particle with water, it added and disperse|distributed to 500 weight part of distilled water, the particle|grain liquid mixture (H) was obtained.

Next, the said silver plating liquid (E) was dripped gradually to the particle|grain liquid mixture (H) of the dispersed state adjusted to 60 degreeC, and electroless silver plating was performed. The dropping rate of the silver plating solution (E) was 10 mL/min, and the dropping time was 30 minutes, and electroless silver plating was performed. Then, the said plating liquid (F) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (F) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During dripping of the plating liquid (F) for projection formation, silver plating was performed, disperse|distributing the generated silver projection nuclei with ultrasonic stirring (projection|protrusion formation process). Then, a nickel-tungsten-boron alloy and a silver metal part (thickness of the whole metal part in a part without a convex part: 0.1 micrometer) on the surface of substrate particle A by taking out particle|grains by filtration, washing with water, and drying It was arrange|positioned, it has a some convex part on the surface, and the metal containing particle|grains provided with the metal part which has a some processus|protrusion on the surface of a convex part were obtained.

(Example 9)

The suspension (B) obtained in Example 1 was put into a solution containing 50 g/L of nickel sulfate, 30 ppm of thallium nitrate, and 20 ppm of bismuth nitrate to obtain a particle mixture (C).

As an electroless nickel-tungsten-boron alloy plating solution, a mixed solution containing 100 g/L of nickel sulfate, 2 g/L of sodium tungstate, 30 g/L of dimethylamine borane, 10 ppm of bismuth nitrate and 30 g/L of trisodium citrate is used with sodium hydroxide. An electroless nickel-tungsten-boron alloy plating solution (D) adjusted to pH 6 was prepared.

In addition, as an electroless gold plating solution, potassium gold cyanide 30 g/L, potassium cyanide 2 g/L, trisodium citrate 30 g/L, ethylenediaminetetraacetic acid 15 g/L, potassium hydroxide 10 g/L, and dimethylamine borane 20 g/L are included. A gold plating solution (E) in which the pH of the mixed solution was adjusted to 8.0 with potassium hydroxide was prepared.

Further, a plating solution (F) (pH 10.0) for forming protrusions containing 30 g/L of sodium borohydride and 0.5 g/L of sodium hydroxide was prepared.

The electroless nickel-tungsten-boron alloy plating solution (D) was gradually added dropwise to the particle mixture solution (C) in a dispersed state adjusted to 60°C to perform electroless nickel-tungsten-boron alloy plating. The electroless nickel-tungsten-boron alloy plating solution (D) was subjected to electroless nickel-tungsten-boron alloy plating at a dropping rate of 15 mL/min and a dropping time of 60 minutes. In this way, the nickel- tungsten- boron alloy metal part is arrange|positioned on the surface of the substrate particle A, and the particle|grain (G) provided with the metal part which has a convex part in the surface was obtained.

Then, a nickel- tungsten-boron alloy metal part is arrange|positioned on the surface of the said substrate particle A by taking out particle|grains by filtering suspension (G), and washing with water, and the particle|grain provided with the metal part which has a convex part on the surface was obtained. After sufficiently washing this particle with water, it added and disperse|distributed to 500 weight part of distilled water, the particle|grain liquid mixture (H) was obtained.

Then, the electroless gold plating solution (E) was gradually added dropwise to the particle mixture solution (H) in a dispersed state adjusted to 60°C to perform electroless gold plating. The electroless gold plating solution (E) was subjected to electroless gold plating at a dropping rate of 10 mL/min and a dropping time of 30 minutes. Then, the said plating liquid (F) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (F) for projection formation was 1 mL/min, and the dripping time was 5 minutes, and projection formation was performed. During the dropwise addition of the plating solution for forming protrusions (F), gold plating was performed while the generated gold protrusion nuclei were dispersed by ultrasonic stirring (protrusion forming step). Then, a nickel-tungsten-boron alloy and gold metal part (the thickness of the whole metal part in a part without a convex part: 0.1 micrometer) on the surface of substrate particle A by taking out particle|grains by filtration, washing with water, and drying It was arrange|positioned, it has a some convex part on the surface, and the metal containing particle|grains provided with the metal part which has a some processus|protrusion on the surface of a convex part were obtained.

(Example 10)

The suspension (B) obtained in Example 1 was put in the solution containing 20 g/L of copper sulfate and 30 g/L of ethylenediamine tetraacetic acid, and the particle|grain liquid mixture (C) was obtained.

In addition, as an electroless copper plating solution, a copper plating solution obtained by adjusting pH 10.5 with ammonia to a mixed solution containing 250 g/L of copper sulfate, 150 g/L of ethylenediaminetetraacetic acid, 100 g/L of sodium gluconate and 50 g/L of formaldehyde (D ) was prepared.

In addition, as an electroless tin plating solution, 20 g/L of tin chloride, 50 g/L of nitrilotriacetic acid, 2 g/L of thiourea, 1 g/L of thiomalic acid, 7.5 g/L of ethylenediaminetetraacetic acid, and 15 g/L of titanium trichloride are included. A tin plating solution (E) was prepared in which the pH of the mixed solution was adjusted to 7.0 with sulfuric acid.

In addition, a plating solution (F) (pH 7.0) for forming projections containing 100 g/L of dimethylamine borane was prepared.

The said copper plating liquid (D) was dripped gradually to the particle|grain liquid mixture (C) in a dispersed state adjusted to 55 degreeC, and electroless copper plating was performed. The dripping rate of the copper plating solution (D) was 30 mL/min, and the dripping time was 30 minutes, and electroless copper plating was performed. Then, particle|grains were taken out by filtration, and the copper metal part is arrange|positioned on the surface of the substrate particle A in this way, and the particle|grain liquid mixture (G) containing the particle|grain provided with the metal part which has a convex part in the surface was obtained.

Then, a copper metal part was arrange|positioned on the surface of the said substrate particle A by taking out particle|grains by filtering the particle|grain liquid mixture (G), and washing with water, and the particle|grain provided with the metal part which has a convex part in the surface was obtained. After sufficiently washing this particle with water, it added and disperse|distributed to 500 weight part of distilled water, the particle|grain liquid mixture (H) was obtained.

Then, the said tin plating liquid (E) was dripped gradually to the particle|grain mixture (H) in a dispersed state adjusted to 60 degreeC, and electroless tin plating was performed. The dropping rate of the tin plating liquid (E) was 10 mL/min, and the dripping time was 30 minutes, and electroless tin plating was performed. Then, the said plating liquid (F) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (F) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During the dropwise addition of the plating solution for forming protrusions (F), tin plating was performed while the generated tin protrusion nuclei were dispersed by ultrasonic stirring (protrusion forming step). Then, copper and a tin metal part (thickness of the whole metal part in a part without a convex part: 0.1 micrometer) is arrange|positioned on the surface of substrate particle A by taking out particle|grains by filtration, washing with water, and drying, the surface A metal-containing particle having a plurality of convex portions and a metal portion having a plurality of projections on the surface of the convex portions was obtained.

(Example 11)

(1) Preparation of silicone oligomers

1 part by weight of 1,3-divinyltetramethyldisiloxane and 20 parts by weight of a 0.5% by weight p-toluenesulfonic acid aqueous solution were placed in a 100 ml separable flask installed in a warm bath. After stirring at 40° C. for 1 hour, 0.05 parts by weight of sodium hydrogen carbonate was added. Then, 10 weight part of dimethoxymethylphenylsilane, 49 weight part of dimethyldimethoxysilane, 0.6 weight part of trimethylmethoxysilane, and 3.6 weight part of methyltrimethoxysilane were added, and it stirred for 1 hour. Then, 1.9 weight part of 10 weight% potassium hydroxide aqueous solution was added, and it stirred and reacted for 10 hours, heating up to 85 degreeC and reducing pressure with an aspirator. After completion of the reaction, the temperature was returned to normal pressure, cooled to 40°C, 0.2 parts by weight of acetic acid was added, and the mixture was left still in a separatory funnel for 12 hours or more. The silicone oligomer was obtained by taking out the lower layer after two-layer separation and refine|purifying with an evaporator.

(2) Production of silicone particle material (including organic polymer)

A solution A was prepared in which 0.5 parts by weight of tert-butyl-2-ethylperoxyhexanoate (polymerization initiator, "Perbutyl O" manufactured by Nichiyo Co., Ltd.) was dissolved in 30 parts by weight of the obtained silicone oligomer. Further, to 150 parts by weight of ion-exchanged water, a 40% by weight aqueous solution of lauryl sulfate triethanolamine salt (emulsifier) and 0.8 parts by weight of polyvinyl alcohol (degree of polymerization: about 2000, degree of saponification: 86.5 to 89 mol%, manufactured by Nippon Kosei Chemicals Co., Ltd.) 80 parts by weight of a 5% by weight aqueous solution of "gosenol GH-20") was mixed to prepare an aqueous solution B. After putting the said solution A into the separable flask installed in the hot bath, the said aqueous solution B was added. Then, emulsification was performed by using a Shirasu Porous Glass (SPG) film|membrane (average pore diameter of about 1 micrometer). Then, it heated up to 85 degreeC and superposition|polymerization was performed for 9 hours. The entire amount of the particles after polymerization was washed with water by centrifugation and freeze-dried. After drying, the aggregates of the particles were pulverized with a ball mill until the target ratio (average secondary particle diameter/average primary particle diameter) was obtained, and silicon particles (substrate particles B) having a particle diameter of 3.0 µm were obtained.

The said substrate particle A was changed into the said substrate particle B, it carried out similarly to Example 1, the metal part was formed, and the metal containing particle was obtained.

(Example 12)

Silicone particles (substrate particles C) having a particle diameter of 3.0 µm were obtained by using both terminal acrylic silicone oil (“X-22-2445” manufactured by Shin-Etsu Chemical Co., Ltd.) instead of the silicone oligomer.

The said substrate particle A was changed into the said substrate particle C, it carried out similarly to Example 1, the metal part was formed, and the metal containing particle was obtained.

(Example 13)

Pure copper particle ("HXR-Cu" by Nippon Atomization Chemical Corporation, particle diameter 2.5 micrometers) was prepared as the substrate particle D.

The said substrate particle A was changed into the said substrate particle D, it carried out similarly to Example 1, the metal part was formed, and the metal containing particle was obtained.

(Example 14)

A pure silver particle (2.5 micrometers in particle diameter) was prepared as substrate particle E.

The said substrate particle A was changed into the said substrate particle E, it carried out similarly to Example 1, the metal part was formed, and the metal containing particle was obtained.

(Example 15)

Only the substrate particle A and the particle diameter differed, and the particle diameter prepared the substrate particle F which is 2.0 micrometers.

The said substrate particle A was changed into the said substrate particle F, it carried out similarly to Example 1, the metal part was formed, and the metal containing particle was obtained.

(Example 16)

Only the substrate particle A and the particle diameter differed, and the particle diameter prepared the substrate particle G which is 10.0 micrometers.

The said substrate particle A was changed into the said substrate particle G, it carried out similarly to Example 1, the metal part was formed, and the metal containing particle was obtained.

(Example 17)

Only the substrate particle A and a particle diameter differed, and the particle diameter prepared the substrate particle H which is 50.0 micrometers.

The said substrate particle A was changed into the said substrate particle H, it carried out similarly to Example 1, the metal part was formed, and the metal containing particle was obtained.

(Example 18)

In a 1000 mL separable flask equipped with a 4-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N,N,N-trimethyl-N-2-methacryloyloxy A monomer composition containing 1 mmol of ethylammonium chloride and 1 mmol of 2,2'-azobis(2-amidinopropane)dihydrochloride is weighed with ion-exchanged water so that the solid content is 5% by weight, followed by stirring at 200rpm, Polymerization was performed for 24 hours at 70°C under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface and having an average particle diameter of 220 nm and a CV value of 10%.

The insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of the insulating particles.

10 g of the metal-containing particles obtained in Example 1 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration with a 3 mu m mesh filter, further washing with methanol and drying were performed to obtain metal-containing particles to which insulating particles adhered.

As a result of observation with a scanning electron microscope (SEM), only one coating layer of insulating particles was formed on the surface of the metal-containing particles. The coverage was 30% as a result of calculating the coverage area of the insulating particle with respect to the area of 2.5 micrometers from the center of a metal-containing particle|grain (namely, the projected area of the particle diameter of an insulating particle) by image analysis.

(Example 19)

The suspension (B) obtained in Example 1 was put in the solution containing 50 g/L of nickel sulfate, 30 ppm of thallium nitrate, and 20 ppm of bismuth nitrate, and the particle|grain liquid (C) was obtained.

An electroless nickel-phosphorus alloy plating solution, wherein a mixed solution containing 100 g/L of nickel sulfate, 30 g/L of sodium hypophosphite, 10 ppm of bismuth nitrate and 30 g/L of trisodium citrate is adjusted to pH 6 with sodium hydroxide. A phosphorus alloy plating solution (D) was prepared.

In addition, as an electroless silver plating solution, a silver plating solution (E) in which a mixed solution of 30 g/L silver nitrate, 100 g/L succinimide, and 20 g/L formaldehyde was adjusted to pH 8.0 with aqueous ammonia was prepared.

In addition, a plating solution (F) (pH 12.0) for forming protrusions containing 130 g/L of sodium hypophosphite and 0.5 g/L of sodium hydroxide was prepared.

The electroless nickel-phosphorus alloy plating solution (D) was gradually added dropwise to the particle mixture solution (C) in a dispersed state adjusted to 65°C to perform electroless nickel-phosphorus alloy plating. The electroless nickel-phosphorus alloy plating solution (D) was subjected to electroless nickel-phosphorus alloy plating at a dropping rate of 15 mL/min and a dropping time of 60 minutes. In this way, the nickel- phosphorus alloy metal part is arrange|positioned on the surface of the substrate particle A, and the particle|grain liquid (G) containing the particle|grain provided with the metal part which has a convex part in the surface was obtained.

Then, the particle|grains were taken out by filtering the particle liquid mixture (G), and by washing with water, the nickel- phosphorus alloy metal layer is arrange|positioned on the surface of the said substrate particle A, and the particle|grain provided with the metal part which has a convex part in the surface was obtained. After sufficiently washing this particle with water, it added and disperse|distributed to 500 weight part of distilled water, the particle|grain liquid mixture (H) was obtained.

Next, the said silver plating liquid (E) was dripped gradually to the particle|grain liquid mixture (H) of the dispersed state adjusted to 60 degreeC, and electroless silver plating was performed. The dropping rate of the silver plating solution (E) was 10 mL/min, and the dropping time was 30 minutes, and electroless silver plating was performed. Then, the said plating liquid (F) for projection formation was dripped gradually, and projection formation was performed. The dropping rate of the plating liquid (F) for projection formation was 1 mL/min, and the dripping time was 10 minutes, and projection formation was performed. During dripping of the plating liquid (F) for projection formation, silver plating was performed, disperse|distributing the generated silver projection nuclei with ultrasonic stirring (projection|protrusion formation process). Then, a nickel- phosphorus alloy and a silver metal part (the thickness of the whole metal part in a part without a convex part: 0.1 micrometer) are arrange|positioned on the surface of substrate particle A by taking out particle|grains by filtration, washing with water, and drying There was obtained a metal-containing particle having a plurality of projections on the surface, and a metal portion having a plurality of projections on the surface of the projections.

(Example 20)

About the metal-containing particle|grains obtained in Example 1, the yellowing prevention process was performed using "New Dyne Silver" manufactured by Yamato Chemicals Co., Ltd. as a silver discoloration inhibitor.

After dispersing 10 parts by weight of the metal-containing particles obtained in Example 1 to 100 parts by weight of an isopropyl alcohol solution containing 10% by weight of Nudyne Silver using an ultrasonic disperser, the solution is filtered to contain a metal with an anti-sulfurization film formed. particles were obtained.

(Example 21)

The metal-containing particles obtained in Example 1 were subjected to an anti-sulfurization treatment using a 2-mercaptobenzothiazole solution as a silver anti-sulfurization agent.

After dispersing 10 parts by weight of the metal-containing particles obtained in Example 1 to 100 parts by weight of an isopropyl alcohol solution containing 0.5% by weight of 2-mercaptobenzothiazole using an ultrasonic disperser, the solution is filtered to prevent sulfurization film. The formed metal-containing particles were obtained.

(Comparative Example 1)

After disperse|distributing 10 weight part of said substrate particles A to 100 weight part of alkali solutions containing 5 weight% of palladium catalyst liquids using the ultrasonic disperser, the substrate particle A was taken out by filtering a solution. Then, the substrate particle A was added to 100 weight part of dimethylamine borane 1 weight% solution, and the surface of the substrate particle A was activated. The dispersion liquid (A) was obtained by adding and disperse|distributing the substrate particle A by which the surface was activated enough to 500 weight part of distilled water, after washing with water.

Then, 1 g of metallic nickel particle slurry ("2020SUS" manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter of 150 nm) is added to the dispersion (A) over 3 minutes, and the suspension (B) containing the substrate particles A to which the core substance adheres. got

The suspension (B) was put in a solution containing 50 g/L of nickel sulfate, 30 ppm of thallium nitrate, and 20 ppm of bismuth nitrate to obtain a particle mixture (C).

Further, a nickel plating solution (D) (pH 6.5) containing 200 g/L of nickel sulfate, 85 g/L of sodium hypophosphite, 30 g/L of sodium citrate, 50 ppm of thallium nitrate and 20 ppm of bismuth nitrate was prepared.

The nickel plating solution (D) was gradually added dropwise to the particle mixture (C) in a dispersed state adjusted to 50°C to perform electroless nickel plating. The dropping rate of the nickel plating solution (D) was 25 mL/min, and the dropping time was 60 minutes, and electroless nickel plating was performed (Ni plating process). Then, a nickel-phosphorus alloy metal part is arrange|positioned on the surface of the substrate particle A by taking out particle|grains by filtering, washing with water, and drying, and the metal containing particle alloy provided with the metal part provided with the metal part which has a processus|protrusion on the surface. (The thickness of the whole metal part in the part without a processus|protrusion: 0.1 micrometer) was obtained.

(Comparative Example 2)

After disperse|distributing 10 weight part of substrate particles A to 100 weight part of alkali solutions containing 5 weight% of palladium catalyst liquids using the ultrasonic disperser, the substrate particle A was taken out by filtering a solution. Then, the substrate particle A was added to 100 weight part of dimethylamine borane 1 weight% solution, and the surface of the substrate particle A was activated. Suspension (A) was obtained by adding and disperse|distributing the substrate particle A by which the surface was activated sufficiently by adding and disperse|distributing to 500 weight part of distilled water, after washing with water.

The suspension (A) was put in a solution containing 50 g/L of nickel sulfate, 30 ppm of thallium nitrate, and 20 ppm of bismuth nitrate to obtain a particle mixture (B).

In addition, a plating solution (C) (pH 11.0) for forming protrusions containing 300 g/L of sodium hypophosphite and 10 g/L of sodium hydroxide was prepared.

Further, a nickel plating solution (D) (pH 6.5) containing 200 g/L of nickel sulfate, 85 g/L of sodium hypophosphite, 30 g/L of sodium citrate, 50 ppm of thallium nitrate and 20 ppm of bismuth nitrate was prepared.

The above-mentioned plating solution for forming projections (C) was gradually added dropwise to the particle mixture (B) in a dispersed state adjusted to 50°C to form projections. The dropping rate of the plating liquid (C) for projection formation was 20 mL/min, and the dripping time was 5 minutes, and projection formation was performed. During the dropwise addition of the plating solution for forming protrusions (C), nickel plating was performed while the generated Ni protrusion nuclei were dispersed by ultrasonic stirring (protrusion forming step). In this way, a dispersion of Ni protrusion nuclei and particle mixture (E) was obtained.

Thereafter, the nickel plating solution (D) was gradually added dropwise to the dispersed Ni protrusion nucleus and particle mixture (E), and electroless nickel plating was performed. The dropping rate of the nickel plating solution (D) was 25 mL/min, and the dropping time was 60 minutes, and electroless nickel plating was performed. During the dropwise addition of the nickel plating solution (D), nickel plating was performed while the generated Ni protrusion nuclei were dispersed by ultrasonic stirring (Ni plating step). Then, a nickel- phosphorus alloy metal part is arrange|positioned on the surface of the substrate particle A by taking out particle|grains by filtration, washing with water, and drying, and metal containing particle|grains (part without a processus|protrusion) provided with the metal part which has a processus|protrusion on the surface. The total thickness of the metal part in: 0.1 µm) was obtained.

(evaluation)

(1) Measuring the height of the convex part and the protrusion

The obtained metal-containing particle|grains were added and disperse|distributed to "Technobit 4000" by Kulzer so that content might be 30 weight%, and the embedding resin for metal-containing particle|grain test|inspection was produced. The cross section of the metal-containing particles was cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the metal-containing particles dispersed in the embedding resin for inspection.

Then, using a field emission transmission electron microscope (FE-TEM) ("JEM-ARM200F" manufactured by Nippon Electronics Co., Ltd.), the image magnification was set to 50,000 times, 20 metal-containing particles were randomly selected, and each metal-containing The protrusions and projections of the particles were observed. The height of the convex part and processus|protrusion in the obtained metal-containing particle|grains was measured, and it was arithmetic averaged and it was set as the average height of the convex part and processus|protrusion.

(2) Measurement of the average diameter of the base of the protrusion

The obtained metal-containing particle|grains were added and disperse|distributed to "Technobit 4000" by Kulzer so that content might be 30 weight%, and the embedding resin for metal-containing particle|grain test|inspection was produced. The cross section of the metal-containing particles was cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the metal-containing particles dispersed in the embedding resin for inspection.

Then, using a field emission transmission electron microscope (FE-TEM) ("JEM-ARM200F" manufactured by Nippon Electronics Co., Ltd.), the image magnification was set to 50,000 times, 20 metal-containing particles were randomly selected, and each metal-containing The convex portions and protrusions of the particles were observed. The diameters of the protrusions and the bases of the protrusions in the obtained metal-containing particles were measured and arithmetic averaged to obtain the average diameters of the protrusions and protrusions.

(3) Observation of the shape of convex portions and projections

Using a scanning electron microscope (FE-SEM), the image magnification was set to 25000 times, 20 metal-containing particles were randomly selected, and the convex portions and protrusions of each metal-containing particle were observed, and all the convex portions and The type of shape to which the protrusion belongs was investigated.

(4) Average measurement of apex angles of convex portions and projections

The obtained metal-containing particle|grains were added and disperse|distributed to "Technobit 4000" by Kulzer so that content might be 30 weight%, and the embedding resin for metal-containing particle|grain test|inspection was produced. The cross section of the metal-containing particles was cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the metal-containing particles dispersed in the embedding resin for inspection.

Then, using a field emission transmission electron microscope (FE-TEM) (“JEM-ARM200F” manufactured by Nippon Electronics Co., Ltd.), the image magnification was set to 1 million times, 20 metal-containing particles were randomly selected, and each metal-containing The protrusions of the particles were observed. The vertex angles of the convex portions and the projections in the obtained metal-containing particles were measured, and they were arithmetic averaged to obtain an average of the vertex angles of the convex portions and the projections.

(5) Measurement of the average diameter at the central position of the height of the convex portion and the projection

The obtained metal-containing particle|grains were added and disperse|distributed to "Technobit 4000" by Kulzer so that content might be 30 weight%, and the embedding resin for metal-containing particle|grain test|inspection was produced. The cross section of the metal-containing particles was cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the metal-containing particles dispersed in the embedding resin for inspection.

Then, using a field emission transmission electron microscope (FE-TEM) ("JEM-ARM200F" manufactured by Nippon Electronics Co., Ltd.), the image magnification was set to 50,000 times, 20 metal-containing particles were randomly selected, and each metal-containing The protrusions of the particles were observed. The diameters of the protrusions and the bases of the protrusions in the obtained metal-containing particles were measured and arithmetic averaged to determine the average diameter at the central position of the heights of the protrusions and protrusions.

(6) Measurement of the ratio of the number of needle-like convexities and projections

Using a scanning electron microscope (FE-SEM), the image magnification was set to 25000 times, 20 metal-containing particles were randomly selected, and the protrusions and projections of each metal-containing particle were observed. All the convex parts and projections are evaluated whether the convex part shape and the projection shape are needle-like tapering toward the tip, The minor shape and the protrusion shape were classified into convex parts and protrusions that were not formed by needles that were tapered toward the end. In this way, per one metal-containing particle, 1) the number of convex portions and projections formed by the tapering needles, and 2) the number of projections and projections not formed by the tapering needle shape toward the tip The number was counted. The ratio X of the number of 1) needle-shaped convex portions and projections in 100% of the total number of projections in 1) and 2) was calculated.

(7) Measurement of the thickness of the entire metal part in the convex part and the part without protrusion

The obtained metal-containing particle|grains were added and disperse|distributed to "Technobit 4000" by Kulzer so that content might be 30 weight%, and the embedding resin for metal-containing particle|grain test|inspection was produced. The cross section of the metal-containing particles was cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the metal-containing particles dispersed in the embedding resin for inspection.

Then, using a field emission transmission electron microscope (FE-TEM) ("JEM-ARM200F" manufactured by Nippon Electronics Co., Ltd.), the image magnification was set to 50,000 times, 20 metal-containing particles were randomly selected, and each metal-containing The metal part was observed in the part where there was no protrusion of particle|grains. In the obtained metal-containing particles, the thickness of the entire metal portion in the non-projection-free portion was measured, and it was arithmetic averaged to obtain a thickness (average thickness) (described in the above examples and comparative examples).

(8) Compressive modulus of metal-containing particles (10% K value)

The said compressive modulus (10% K-value) of the obtained metal-containing particle|grains was measured using the micro compression tester ("Fischer Scope H-100" manufactured by Fischer) by the method mentioned above on 23 degreeC conditions. A 10% K value was obtained.

(9) Evaluation of the face lattice of the metal part

Using an X-ray diffraction apparatus ("RINT2500VHF" manufactured by Rigaku Electric Co., Ltd.), the peak intensity ratio of the diffraction line unique to the apparatus depending on the diffraction angle was calculated. The ratio of the diffraction peak intensity in the (111) orientation to the diffraction peak intensity of the entire diffraction line of the gold layer (the ratio of the (111) plane) was calculated.

(10) Melting and solidification state of the tip of the projection of the metal part in the bonded structure A

The obtained metal-containing particle|grains were added and disperse|distributed to the Mitsui Chemicals make "Struct Bond XN-5A" so that content might be 10 weight%, and the anisotropic electrically conductive paste was produced.

A transparent glass substrate having a copper electrode pattern having an L/S of 30 µm/30 µm on the upper surface was prepared. Further, a semiconductor chip having a gold electrode pattern having an L/S of 30 µm/30 µm on the lower surface was prepared.

On the said transparent glass substrate, the anisotropic electrically conductive paste immediately after preparation was coated so that it might become 30 micrometers in thickness, and the anisotropic electrically conductive paste layer was formed. Next, on the anisotropic conductive paste layer, the said semiconductor chip was laminated|stacked so that electrodes might face each other. After that, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 250 ° C, a pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 0.5 MPa is applied to cure the anisotropic conductive paste layer at 250 ° C. Structure A was obtained. In order to obtain the bonded structure A, it was connected between electrodes by the low pressure of 0.5 MPa.

The obtained bonded structure was put into "Technobit 4000" by Kulzer, and it hardened, and the embedding resin for bonded structure inspection was produced. The cross section of the metal-containing particle was cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the bonded structure in the resin for inspection.

And by cross-sectional observation of the obtained bonded structure A using a scanning electron microscope (FE-SEM), it was determined whether the tip of the processus|protrusion of the metal part of a metal-containing particle|grain had melted, after which it had solidified.

[Criteria for judging the melted and solidified state of the tip of the projection of the metal part]

A: The tip of the projection of the metal part is melted and then solidified

B: The tip of the projection of the metal part is not solidified after being melted

(11) Bonding state of the projections of the metal part in the bonded structure A

Bonded structure A obtained by evaluation of said (10) WHEREIN: The bonding state of the processus|protrusion of a metal part was determined by cross-sectional observation of bonded structure A.

[Criteria for judging the joint state of the projections of the metal part]

A: In the connection part, the tip of the projection of the metal part in the metal-containing particle is melted and then solidified, and is joined to the electrode and other metal-containing particles

B: In the connection part, the tip of the projection of the metal part in the metal-containing particle is melted and then solidified, and is not joined with the electrode and other metal-containing particles

(12) Connection reliability in bonded structure A

The connection resistance between the upper and lower electrodes of 15 bonded structures A obtained by evaluation of said (10) was measured by the 4-probe method. The average value of connection resistance was computed. In addition, from the relationship of voltage = current x resistance, the connection resistance can be calculated|required by measuring the voltage when a constant current flows. Connection reliability was judged according to the following criteria.

[Criteria for judgment of connection reliability]

○○○: Connection resistance is 1.0Ω or less

○○: Connection resistance greater than 1.0 Ω and less than 2.0 Ω

○: Connection resistance greater than 2.0 Ω and less than 3.0 Ω

△: Connection resistance exceeds 3.0 Ω and less than or equal to 5 Ω

×: Connection resistance exceeds 5 Ω

(13) Melting and solidification state of the tip of the projection of the metal part in the bonded structure B

The obtained metal-containing particles were added and dispersed in "ANP-1" manufactured by Nippon Speria Co., Ltd. (including metal atom-containing particles) so that the content was 5% by weight to prepare a sintered silver paste.

As a 1st connection object member, the power semiconductor element in which Ni/Au plating was given to the connection surface was prepared. As a 2nd connection object member, the aluminum nitride board|substrate in which Cu plating was given to the connection surface was prepared.

On the second connection object member, the sintered silver paste was applied to a thickness of about 70 µm, and a silver paste layer for connection was formed. Then, the said 1st connection object member was laminated|stacked on the silver paste layer for a connection, and the laminated body was obtained.

The obtained laminate is preheated on a hot plate at 130° C. for 60 seconds, and then the laminate is heated at 300° C. under a pressure of 10 MPa for 3 minutes to sinter and sinter the metal atom-containing particles included in the sintered silver paste. The connection part containing water and metal containing particle|grains was formed, the said 1st, 2nd connection object member was joined with this sintered material, and the bonded structure B was obtained.

The obtained bonded structure was put into "Technobit 4000" by Kulzer, and it hardened, and the embedding resin for bonded structure inspection was produced. The cross section of the metal-containing particles was cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the bonded structure in the embedding resin for inspection.

And by cross-sectional observation of the obtained bonded structure B using a scanning electron microscope (FE-SEM), it was judged whether the front-end|tip of the processus|protrusion of the metal part of a metal-containing particle|grain was solidified after melt|melting.

[Criteria for judging the melted and solidified state of the tip of the projection of the metal part]

A: The tip of the projection of the metal part is melted and then solidified

B: The tip of the projection of the metal part is not solidified after being melted

(14) Bonding state of the projections of the metal part in the bonded structure B

Bonded structure B obtained by evaluation of said (13) WHEREIN: The bonding state of the processus|protrusion of a metal part was determined by cross-sectional observation of bonded structure B.

[Criteria for judging the joint state of the projections of the metal part]

A: In the connection part, the tip of the projection of the metal part in the metal-containing particle is melted and then solidified, and is joined to the electrode and other metal-containing particles

B: In the connection part, the tip of the projection of the metal part in the metal-containing particle is melted and then solidified, and is not joined with the electrode and other metal-containing particles

(15) Connection reliability in bonded structure B

The bonded structure B obtained in the evaluation of the above (13) is put into a cold and thermal shock tester (manufactured by SPEC: TSA-101S-W), the minimum temperature is -40°C for a holding time of 30 minutes, and the maximum temperature is 200°C for a holding time of 30 The bonding strength was measured with a shear strength tester (manufactured by Lesca Corporation: STR-1000) after 3000 cycles with the treatment conditions as 1 cycle. Connection reliability was judged according to the following criteria.

[Criteria for judgment of connection reliability]

○○○: Bond strength of 50 MPa or more

○○: Joint strength greater than 40 MPa and less than or equal to 50 MPa

○: bonding strength greater than 30 MPa and less than or equal to 40 MPa

△: bonding strength greater than 20 MPa and less than or equal to 30 MPa

x: bonding strength is 20 MPa or less

(16) Contact resistance value of member for continuity inspection

10 parts by weight of the silicone copolymer, 90 parts by weight of the obtained metal-containing particles, 1 part by weight of an epoxysilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBE-303") and 36 parts by weight of isopropyl alcohol are blended, and homodisper After stirring at 1000 rpm for 20 minutes using a metal-containing particle, an electrically-conductive material containing metal-containing particles and a binder was prepared by defoaming using "Rentaro ARE250" manufactured by Thinky Co., Ltd.

The silicone-based copolymer was polymerized by the following method. 162 g (628 mmol) of 4,4'-dicyclohexylmethane diisocyanate (manufactured by Degus Corporation), polydimethylsiloxane modified with an amino group at one end ("TSF4709", manufactured by Momentive) 900 g (molecular weight 10000) (molecular weight 10000) in a metal kneader having a capacity of 2 L ) and dissolved at 70 to 90°C, followed by stirring for 2 hours. Then, 65 g (625 mmol) of neopentyl glycol (manufactured by Mitsubishi Gas Chemical) was slowly added and kneaded for 30 minutes, and then unreacted neopentyl glycol was removed under reduced pressure. The obtained silicone copolymer was used by dissolving in isopropyl alcohol so that it might become 20 weight%. In addition, loss|disappearance of an isocyanate group was confirmed by the IR spectrum. The obtained silicone copolymer WHEREIN: The silicone content was 80 weight%, the weight average molecular weight was 25000, the SP value was 7.8, and the SP value of the repeating unit of the structure (polyurethane) having a polar group was 10.

Next, as a base material (sheet-like base material formed of an insulating material) of the member for conduction inspection, a silicone rubber was prepared. The size of the silicone rubber is 25mm in width, 25mm in length, and 1mm in thickness. In the silicone rubber, a total of 400 cylindrical through-holes with a diameter of 0.5 mm formed by laser processing, 20 vertically and 20 horizontally, are formed.

The said electrically-conductive material was coated using the knife coater on the silicone rubber which has a through-hole, and the electrically-conductive material was filled in the through-hole. Subsequently, the silicone rubber filled with the conductive material in the through hole was dried in an oven at 50° C. for 10 minutes, and then further dried at 100° C. for 20 minutes to obtain a member for continuity inspection with a thickness of 1 mm.

The contact resistance value of the obtained member for continuity|electrical_connection test|inspection was measured using the contact resistance measuring system ("MS7500" by the Fact-K company). The contact resistance measurement was carried out by pressing from a perpendicular direction to the conductive part of the member for conduction inspection obtained with a load of 15 gf with a platinum probe having a diameter of 0.5 mm. At that time, 5V was applied with a low resistance meter ("MODEL3566" by Tsuruga Denki Corporation), and the contact resistance value was measured. The average value of the contact connection resistance value which measured the electroconductive part of 5 places was computed. The contact resistance value was determined based on the following reference.

[Criteria for judgment of contact resistance value]

○○: The average value of the connection resistance is 50.0 mΩ or less

○: Average value of connection resistance exceeds 50.0 mΩ and less than 100.0 mΩ

△: The average value of the connection resistance exceeds 100.0 mΩ and 500.0 mΩ or less

×: The average value of the connection resistance exceeds 500.0 mΩ

(17) Repeated reliability test of members for continuity inspection

The member for conduction inspection of evaluation of the contact resistance value of said (16) member for conduction inspection was prepared.

The repeated reliability test and contact resistance value of the obtained member for conduction inspection were measured using the contact resistance measuring system ("MS7500" by Fact-K company). The repeated reliability test was repeated 1000 times from the perpendicular direction to the conductive portion of the probe sheet obtained under a load of 15 gf with a platinum probe having a diameter of 0.5 mm and pressed. After pressurizing repeatedly 1000 times, 5 V was applied with a low-resistance meter ("MODEL3566" manufactured by Tsuruga Electronics Co., Ltd.), and the contact resistance value was measured. The average value of the contact resistance values which measured 5 electroconductive parts similarly was computed. The contact resistance value was determined based on the following reference.

[Criteria for determining the contact resistance value after repeated pressurization]

○○: The average value of the connection resistance is 100.0 mΩ or less

○: The average value of connection resistance exceeds 100.0 mΩ and below 500.0 mΩ

△: The average value of the connection resistance exceeds 500.0 mΩ and 1000.0 mΩ or less

×: The average value of the connection resistance exceeds 1000.0 mΩ

A composition and a result are shown in Tables 1-5.

In addition, the spherical shape in the convex portion and the projection includes a partial shape of a sphere. Moreover, in Comparative Examples 1 and 2, even if it heated to 400 degreeC, it confirmed that the front-end|tip of a processus|protrusion did not melt|dissolve.

1, 1A, 1B, 1C, 1D, 1E, 1F, 1G… metal-containing particles
1a, 1Aa, 1Ba, 1Ca, 1Da, 1Ea, 1Fa, 1Ga... spin
2… substrate particles
3, 3A, 3B, 3C, 3D, 3E, 3F, 3G… Metal part (metal layer)
3a, 3Aa, 3Ba, 3Ca, 3Da, 3Ea, 3Fa, 3Ga... spin
3BX… metal particles
3CA, 3GA… first metal part
3CB, 3GB… second metal part
3Da, 3Ea, 3Fa, 3Ga... convex
3Db, 3Eb, 3Fb, 3Gb… spin
4E… core material
11… Member for continuity inspection
12… gas
12a… through hole
13… conductive part
21… Member for continuity inspection
22… gas
22a… through hole
23… conductive part
31… BGA board
31A… multilayer substrate
31B… solder ball
32… ammeter
51… connection structure
52... 1st connection target member
52a... first electrode
53… 2nd connection target member
53a… second electrode
54… junction
61... connection structure
62... 1st connection target member
63, 64... 2nd connection target member
65, 66... junction
67… other metal-containing particles
68, 69... heat sink

Claims (23)

substrate particles;
The metal part arrange|positioned on the surface of the said substrate particle is provided,
The metal part has a plurality of projections on the outer surface,
The tip of the protrusion of the metal part is meltable at 400° C. or less, a metal-containing particle. The method according to claim 1, wherein the metal part has a plurality of convex parts on the outer surface,
The metal-containing particle in which the said metal part has the said processus|protrusion on the outer surface of the said convex part. The metal-containing particle according to claim 2, wherein the ratio of the average height of the convex portions to the average height of the projections is 5 or more and 1000 or less. The metal-containing particle according to claim 2 or 3, wherein the average diameter of the base of the convex portion is 3 nm or more and 5000 nm or less. The metal-containing particle according to any one of claims 2 to 4, wherein, out of 100% of the total surface area of the outer surface of the metal portion, the surface area of the portion having the convex portion is 10% or more. The metal-containing particle according to any one of claims 2 to 5, wherein the shape of the convex portion is a needle-like shape or a partial shape of a sphere. The metal-containing particle according to any one of claims 1 to 6, wherein the average of the vertex angles of the projections is 10° or more and 60° or less. The metal-containing particle according to any one of claims 1 to 7, wherein the average height of the projections is 3 nm or more and 5000 nm or less. The metal-containing particle according to any one of claims 1 to 8, wherein the average diameter of the base of the protrusion is 3 nm or more and 1000 nm or less. The metal-containing particle according to any one of claims 1 to 9, wherein the ratio of the average height of the projections to the average diameter of the base of the projections is 0.5 or more and 10 or less. The metal-containing particle according to any one of claims 1 to 10, wherein the shape of the protrusion is a needle-like shape or a partial shape of a sphere. The metal-containing particle according to any one of claims 1 to 11, wherein the material of the protrusion comprises silver, copper, gold, palladium, tin, indium or zinc. The metal-containing particle according to any one of claims 1 to 12, wherein the material of the metal part is not solder. 14. The material according to any one of claims 1 to 13, wherein the material of the metal part is silver, copper, gold, palladium, tin, indium, zinc, nickel, cobalt, iron, tungsten, molybdenum, ruthenium, platinum, rhodium, iridium. , phosphorus or boron. The metal-containing particle according to any one of claims 1 to 14, wherein the tip of the projection of the metal part is meltable at 350°C or less. The metal-containing particle according to claim 15, wherein the tip of the projection of the metal part is meltable at 300°C or less. The metal-containing particle according to claim 16, wherein the tip of the projection of the metal part is meltable at 250°C or less. The metal-containing particle according to claim 17, wherein the tip of the projection of the metal part is meltable at 200°C or less. Claim 1 to claim 18, wherein according to any one of, wherein the compression elastic modulus 100N / mm ² or more 25000N / mm ² or less, the metal-containing particles when compressed 10%. The metal-containing particle according to any one of claims 1 to 19, wherein the substrate particle is a silicon particle. The metal-containing particles according to any one of claims 1 to 20;
A connection material containing a resin. a first connection target member;
a second connection target member;
a connection portion connecting the first connection object member and the second connection object member;
The bonded structure in which the material of the said connection part is the metal containing particle|grains in any one of Claims 1-20, or is a connection material containing the said metal containing particle and resin. A step of disposing the metal-containing particles according to any one of claims 1 to 20, or disposing a connection material comprising the metal-containing particles and a resin between the first connection object member and the second connection object member class,
The metal-containing particles are heated to melt the tip of the protrusion of the metal part and solidify after melting, so that the first connection object member and the second connection object member are connected by the metal-containing particles or the connection material. The manufacturing method of the bonded structure provided with the process of forming the connection part currently being carried out.

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