JP6577723B2 - Conductive particles with insulating particles, conductive material, and connection structure - Google Patents

Description

  The present invention relates to conductive particles with insulating particles that can be used for electrical connection between electrodes, for example. Moreover, this invention relates to the electrically-conductive material and connection structure using the said electroconductive particle with an insulating particle.

  Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In these anisotropic conductive materials, conductive particles are dispersed in a binder resin.

  The anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after disposing an anisotropic conductive material between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be electrically connected by heating and pressing.

  As an example of the conductive particle, Patent Document 1 below includes an insulating particle including a particle having a conductive metal surface and an insulating particle covering the surface of the particle having the conductive metal surface. Conductive particles are disclosed. Patent Document 1 describes that when two or more kinds of insulating particles having different particle diameters are used in combination, small insulating particles enter a gap covered with large insulating particles, thereby improving the coating density. .

JP 2005-44773 A

  In the conductive particles with insulating particles described in Patent Document 1, the conductive metal surface is covered with insulating particles, and therefore, between the vertically adjacent electrodes that should not be connected after the upper and lower conductive connections. Electrical connection can be suppressed. That is, the insulation reliability in the conductively connected connection structure can be improved. In addition, by using two or more kinds of insulating particles having different particle diameters in combination, the small insulating particles are inserted into the gaps covered with the large insulating particles, thereby increasing the coating density, thereby increasing the insulation reliability. be able to. However, Patent Document 1 only describes that small insulating particles are allowed to enter a gap covered with large insulating particles.

  By the way, in recent years, electronic components have been downsized. For this reason, in the wiring connected by the conductive particles in the electronic component, L / S indicating the width of the line (L) in which the wiring is formed and the width of the space (S) in which no wiring is formed is reduced. It is coming. When such fine wiring is formed, if conductive connection is performed using conventional conductive particles with insulating particles, it is difficult to ensure sufficient insulation reliability.

  In addition, when conductive connection is performed using conventional conductive particles with insulating particles, the insulating particles positioned between the conductive particles and the electrode may not be sufficiently removed, and the connection resistance may be increased. That is, conventional conductive particles with insulating particles may not provide sufficient conduction reliability.

  Furthermore, when a connection structure in which conductive connection is performed using conventional conductive particles with insulating particles is exposed to the presence of an acid, the connection resistance between the electrodes may increase.

  An object of the present invention is to improve insulation reliability and conduction reliability in a connection structure in which electrodes are connected to each other. Further, even when the connection structure is exposed to an acid, the connection resistance is kept low. It is to provide conductive particles with insulating particles, and to provide a conductive material and a connection structure using the conductive particles with insulating particles.

  According to a wide aspect of the present invention, the conductive particles, the plurality of first insulating particles disposed on the surface of the conductive particles so as to contact the surface of the conductive particles, and the plurality of first particles Two insulating particles, and the conductive particles cover the base particles, the core material disposed on the surface of the base particles, and the base particles and the core material. A conductive portion disposed on the surface of the base particle, and the core material bulges the outer surface of the conductive portion, whereby the conductive particle has a plurality of protrusions on the surface, At least a part of the second insulating particles is disposed on the surface of the first insulating particles so as not to contact the conductive particles, and the core material is made of an inorganic material or an inorganic material. Conductive particles with insulating particles, which are metal oxides other than the above, are provided.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the material of the core substance is alumina, tungsten, or titania.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the average particle size of the second insulating particles is smaller than the average particle size of the first insulating particles.

  On the specific situation with the electroconductive particle with an insulating particle which concerns on this invention, the average height of the said processus | protrusion is larger than the average particle diameter of a said 1st insulating particle.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the average height of the protrusions is an average particle size of the first insulating particles and an average particle size of the second insulating particles. Less than the sum of

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the first particles are used so that 10% or more of the total number of the second insulating particles does not contact the conductive particles. It is arranged on the surface of the insulating particles.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the second insulating particles are attached to the surface of the first insulating particles through a chemical bond.

  On the specific situation with the electroconductive particle with an insulating particle which concerns on this invention, the said 1st insulating particle has adhered to the surface of the said electroconductive particle through a chemical bond.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the first insulating particles are not arranged on the surface of the conductive particles by a hybridization method, and the second particles Insulating particles are not arranged on the surface of the first insulating particles by the hybridization method.

  According to a wide aspect of the present invention, there is provided a conductive material including the conductive particles with insulating particles described above and a binder resin.

  According to a wide aspect of the present invention, a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connecting portion connecting the second connection target member, wherein the connecting portion is formed of the above-described conductive particles with insulating particles, or the conductive particles with insulating particles and a binder resin. A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles. Is provided.

  The conductive particles with insulating particles according to the present invention include conductive particles and a plurality of first insulating particles disposed on the surface of the conductive particles so as to be in contact with the surface of the conductive particles. A plurality of second insulating particles, wherein the conductive particles are base particles, a core material disposed on the surface of the base particles, the base particles, and the core material. A conductive portion disposed on the surface of the base particle so as to cover the surface, and the core material raises the outer surface of the conductive portion, so that the conductive particle has a plurality of protrusions on the surface. And at least a part of the plurality of second insulating particles are arranged on the surface of the first insulating particles so as not to contact the conductive particles, Since the material is an inorganic substance or a metal oxide excluding an inorganic substance, the conductive with insulating particles according to the present invention In the connection structure obtained by connecting the electrodes with the particles, it is possible to improve the insulation reliability and conduction reliability. Furthermore, even when the connection structure is exposed to the presence of an acid, the connection resistance can be kept low.

FIG. 1 is a cross-sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention. FIG. 3 is a cross-sectional view showing conductive particles with insulating particles according to the third embodiment of the present invention. FIG. 4 is a sectional view showing conductive particles with insulating particles according to the fourth embodiment of the present invention. FIG. 5 is a cross-sectional view showing conductive particles with insulating particles according to the fifth embodiment of the present invention. FIG. 6 is a front sectional view schematically showing a connection structure using the conductive particles with insulating particles shown in FIG. 1.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

(Conductive particles with insulating particles)
FIG. 1 is a sectional view showing conductive particles with insulating particles according to the first embodiment of the present invention.

  The conductive particle 1 with insulating particles shown in FIG. 1 includes conductive particles 2, a plurality of first insulating particles 3, and a plurality of second insulating particles 4.

  The conductive particles 2 have a conductive portion 12 on the outer surface. The 1st insulating particle 3 is arrange | positioned on the surface of the electroconductive particle 2 so that the electroconductive particle 2 may be contacted. At least some of the plurality of second insulating particles 4 are arranged on the surface of the first insulating particles 3 so as not to contact the conductive particles 2. At least a part of the plurality of second insulating particles 4 is disposed on the surface of the first insulating particle 3 so as not to contact the conductive portion 12 in the conductive particle 2. At least a part of the plurality of second insulating particles 4 may be arranged on the surface of the first insulating particles 3 so as to be in contact with the conductive particles 2. All of the plurality of second insulating particles 4 may be disposed on the surface of the first insulating particles 3 so as not to contact the conductive particles 2.

  In addition, the plurality of first insulating particles 3 are disposed on both the portion of the conductive particle 2 where the protrusion 2a is not present and the portion where the protrusion 2a is present.

  The plurality of first insulating particles 3 are in contact with the surface of the conductive particles 2 and are attached to the surface of the conductive particles 2. The plurality of first insulating particles 3 are in contact with the outer surface of the conductive part 12 in the conductive particle 2 and are attached to the outer surface of the conductive part 12. The second insulating particles 4 arranged on the surface of the first insulating particles 3 are in contact with the surface of the first insulating particles 3 and adhere to the surface of the first insulating particles 3. is doing.

  The conductive particle 2 includes a base particle 11 and a conductive portion 12 disposed on the surface of the base particle 11. The conductive part 12 is a conductive layer. The conductive part 12 covers the surface of the base particle 11. The conductive particle 2 is a coated particle in which the surface of the base particle 11 is coated with the conductive portion 12. The conductive particle 2 has a conductive portion 12 on the surface.

  The conductive particle 2 has a plurality of core substances 13 on the surface of the base particle 11. The conductive part 12 covers the base particle 11 and the core substance 13. By covering the core substance 13 with the conductive portion 12, the conductive particles 2 have a plurality of protrusions 2a on the surface. The surface of the conductive portion 12 is raised by the core substance 13, and a plurality of protrusions 2a are formed. The core substance 13 is located inside the plurality of protrusions 2a.

  In the present embodiment, the material of the core substance 13 is an inorganic substance or a metal oxide excluding the inorganic substance. The material of the core substance 13 is the same in the second, third, fourth, and fifth embodiments.

  In the present embodiment, the average height of the protrusions 2 a is larger than the average particle diameter of the first insulating particles 3. Further, the average height of the protrusions 2 a is smaller than the sum of the average particle diameter of the first insulating particles 3 and the average particle diameter of the second insulating particles 4. The average particle diameter of the second insulating particles 4 is smaller than the average particle diameter of the first insulating particles 3. Therefore, for example, when the average particle diameter of the first insulating particles 3 is 300 nm and the average particle diameter of the second insulating particles 4 is 150 nm, the average particle diameter of the first insulating particles 3 is The sum of the average particle diameter of the second insulating particles 4 is 450 nm, and the average height of the protrusions 2a is more than 300 nm and less than 450 nm.

  The tips of at least some of the plurality of second insulating particles 4 are located farther from the center of the conductive particles 2 than the tips of the protrusions 2a. All the tips of the plurality of second insulating particles may be located farther from the center of the conductive particles than the tips of the protrusions. At least some of the tips of the plurality of composites of the first insulating particles 3 and the second insulating particles 4 are located farther from the center of the conductive particles 2 than the tips of the protrusions 2a. All the tips of the plurality of composites of the first insulating particles and the second insulating particles may be located farther from the center of the conductive particles than the tips of the protrusions. The composite has first insulating particles and second insulating particles arranged on the surface of the first insulating particles so as to be in contact with the first insulating particles. The tips of some of the plurality of protrusions 2 a are closer to the center of the conductive particles 2 than the tips of the second insulating particles 4. All the tips of the plurality of protrusions may be closer to the center of the conductive particles than the tips of the second insulating particles.

  FIG. 2 is a sectional view showing conductive particles with insulating particles according to the second embodiment of the present invention.

  A conductive particle 1A with insulating particles shown in FIG. 2 includes conductive particles 2, a plurality of first insulating particles 3A, and a plurality of second insulating particles 4A.

  In the conductive particles 1 with insulating particles and the conductive particles 1A with insulating particles, the first insulating particles 3 and 3A have different sizes, and the second insulating particles 4 and 4A have different sizes. .

  The first insulating particles 3 </ b> A are smaller than the first insulating particles 3. The second insulating particles 4A are smaller than the second insulating particles 4.

  In the second embodiment, the average height of the protrusions 2a is larger than the average particle diameter of the first insulating particles 3A. The average height of the protrusions 2a is larger than the sum of the average particle diameter of the first insulating particles 3A and the average particle diameter of the second insulating particles 4A. The average height of the protrusions 2a is larger than the average particle diameter of the second insulating particles 4A.

  Thus, the average height of the protrusions may be larger than or equal to the sum of the average particle diameter of the first insulating particles and the average particle diameter of the second insulating particles. Accordingly, the average height of the protrusions may be equal to or greater than the sum of the average particle diameter of the first insulating particles and the average particle diameter of the second insulating particles.

  In FIG. 3, the electroconductive particle with an insulating particle which concerns on the 3rd Embodiment of this invention is shown with sectional drawing.

  A conductive particle 1 </ b> B with insulating particles shown in FIG. 3 includes conductive particles 2, a plurality of first insulating particles 3, and a plurality of second insulating particles 4.

  The conductive particles 1 with insulating particles and the conductive particles 1B with insulating particles differ only in the locations where the plurality of second insulating particles 4 are arranged. In the conductive particles 1B with insulating particles, compared to the conductive particles 1 with insulating particles, the conductive particles 1B are arranged on the surface of the first insulating particles 3 so as not to contact the conductive particles 2 and the conductive portions 12. The number of the second insulating particles 4 is relatively small. In the conductive particles 1B with insulating particles, the second conductive particles 2B are in contact with the conductive particles 2 and the conductive portions 12 so as not to contact the first insulating particles 3 as compared with the conductive particles 1 with insulating particles. The number of insulating particles 4 is relatively large.

  Thus, the number of the second insulating particles 4 arranged on the surface of the first insulating particles 3 so as not to contact the conductive particles 2 and the first insulating particles 3 are prevented from contacting. Further, the number of the second insulating particles 4 in contact with the conductive particles 2 and the conductive portion 12 can be changed as appropriate.

  FIG. 4 is a sectional view showing conductive particles with insulating particles according to the fourth embodiment of the present invention.

  A conductive particle with insulating particles 1 </ b> C shown in FIG. 4 includes conductive particles 2 </ b> C, a plurality of first insulating particles 3, and a plurality of second insulating particles 4.

  The conductive particles 2C have a conductive portion 12C on at least the outer surface. The 1st insulating particle 3 is arrange | positioned on the surface of the electroconductive particle 2C so that the electroconductive particle 2C may be contacted. At least some of the plurality of second insulating particles 4 are arranged on the surface of the first insulating particles 3 so as not to contact the conductive particles 2C.

  The conductive particle 2 </ b> C includes base material particles 11, a conductive portion 12 </ b> C disposed on the surface of the base material particle 11, and a plurality of core substances 13 disposed on the surface of the base material particle 11. The conductive particles 2C have a plurality of protrusions 2Ca on the surface.

  The conductive particles 1 with insulating particles and the conductive particles 1C with insulating particles differ only in the conductive particles 2 and 2C. Only the conductive portions 12 and 12C are different between the conductive particles 2 and the conductive particles 2C. That is, in the conductive particle 2, the conductive part 12 having a single layer structure is formed, whereas in the conductive particle 2C, the conductive part having a two layer structure including the first conductive part 12CA and the second conductive part 12CB. A portion 12C is formed.

  The first conductive portion 12CA is an inner layer, and the second conductive portion 12CB is an outer layer. On the surface of the base particle 11, the first conductive portion 12CA is disposed. The second conductive portion 12CB is disposed on the outer surface of the first conductive portion 12CA.

  Thus, the conductive portion 12C may have a multilayer structure such as a two-layer structure.

  FIG. 5 is a sectional view showing conductive particles with insulating particles according to the fifth embodiment of the present invention.

  A conductive particle 1D with insulating particles shown in FIG. 5 includes conductive particles 2, a plurality of first insulating particles 3D, and a plurality of second insulating particles 4D.

  In the conductive particles 1 with insulating particles and the conductive particles 1D with insulating particles, the first insulating particles 3 and 3D have different sizes, and the second insulating particles 4 and 4D have different sizes. .

  The first insulating particles 3D are larger than the first insulating particles 3. The second insulating particles 4 </ b> D are larger than the second insulating particles 4.

  In the fifth embodiment, the average height of the protrusions 2a is smaller than the average particle diameter of the first insulating particles 3D. The average height of the protrusions 2a is smaller than the sum of the average particle diameter of the first insulating particles 3D and the average particle diameter of the second insulating particles 4D. The average height of the protrusions 2a is larger than the average particle diameter of the second insulating particles 4D.

  Thus, the average height of the protrusions may be smaller or the same as the average particle diameter of the first insulating particles. Accordingly, the average height of the protrusions may be equal to or less than the average particle diameter of the first insulating particles.

  In any of the conductive particles with insulating particles included in the present invention, such as the conductive particles with insulating particles 1, 1A, 1B, 1C, 1D, at least some of the plurality of second insulating particles are It arrange | positions on the surface of 1st insulating particle so that it may not contact electroconductive particle. Further, the material of the core substance that makes the outer surface of the conductive part rise is an inorganic substance or a metal oxide excluding the inorganic substance. Of the conductive particles 1, 1A, 1B, 1C, 1D with insulating particles, the conductive particles 1, 1A, 1C with insulating particles are preferable.

  Therefore, when the upper and lower electrodes are electrically connected using the conductive particles with insulating particles, it is possible to suppress electrical connection between the electrodes adjacent in the lateral direction that should not be connected. That is, insulation reliability can be improved. Normally, during conductive connection, a large force that affects the detachment of the first and second insulating particles is applied. As a result, the first and second insulating particles are detached and exposed conductive particles. Contacts the electrode. Furthermore, if the upper and lower electrodes are electrically connected using the conductive particles with insulating particles, the first and second insulating particles located between the conductive particles and the electrodes are sufficiently eliminated. , The connection resistance is lowered. As a result, conduction reliability between the electrodes can be improved.

  In particular, the core material that raises the outer surface of the conductive part is an inorganic substance or a metal oxide excluding the inorganic substance, so that the connection resistance is kept low even when the connection structure is exposed to acid conditions. be able to. In particular, the material of the core substance that bulges the outer surface of the conductive part is alumina, tungsten, or titania, so that the connection resistance can be kept even lower even when the connection structure is exposed to acid conditions. Can do. This is because even if the corrosion of the conductive part exposed to the acid condition occurs, the core substance formed by the inorganic substance or the metal oxide excluding the inorganic substance located inside the conductive part contributes to maintaining the connection resistance. It is thought that. When the conductive particles are compressed, the conductive portion may be cracked. Even if a crack occurs in the conductive part, the corrosion in the conductive part is suppressed, and as a result, the connection resistance can be effectively kept low.

  Furthermore, an oxide film may be formed on the surface of the conductive particles. Further, an oxide film is often formed on the surface of the electrode connected by the conductive particles with insulating particles. When conductive particles with insulating particles having protrusions on the surface of the conductive particles are used, the oxide film can be effectively applied by the protrusions by placing and bonding the conductive particles with insulating particles between the electrodes. Can be eliminated. For this reason, an electrode and an electroconductive part contact more reliably and the connection resistance between electrodes becomes still lower. Furthermore, when the electrodes are connected, the insulating particles between the conductive particles and the electrodes can be effectively eliminated by the protrusions of the conductive particles. For this reason, the conduction | electrical_connection reliability between electrodes becomes still higher.

  From the viewpoint of further increasing the insulation reliability, the conduction reliability, and the insulation reliability against impact, the average height of the protrusions is preferably larger than the average particle diameter of the first insulating particles. The ratio of the average height of the protrusions to the average particle diameter of the first insulating particles (average height of the protrusions / average particle diameter of the first insulating particles) is preferably 1.1 or more, more preferably 1. 0.5 or more, preferably 2.0 or less, more preferably 1.8 or less. When the ratio (average height of protrusions / average particle diameter of first insulating particles) is not less than the above lower limit, the conduction reliability is further enhanced. When the ratio (average height of protrusions / average particle diameter of the first insulating particles) is not more than the above upper limit, the conduction reliability, the insulation reliability, and the insulation reliability against impact are further enhanced.

  From the viewpoint of further improving the conduction reliability, the insulation reliability, and the insulation reliability against impact, the average height of the protrusions is the average particle diameter of the first insulating particles and the average particle diameter of the second insulating particles. Is preferably smaller than the sum of the above. Ratio of the average height of the protrusions to the sum of the average particle diameter of the first insulating particles and the average particle diameter of the second insulating particles (average height of protrusions / average particle diameter of the first insulating particles) And the average particle diameter of the second insulating particles) is preferably 0.3 or more, more preferably 0.5 or more, preferably 0.95 or less, more preferably 0.9 or less, and still more preferably. 0.8 or less. When the ratio (the average height of the projections / the average particle diameter of the first insulating particles and the average particle diameter of the second insulating particles) is equal to or more than the above lower limit, the conduction reliability is further increased. . When the ratio (the average height of the protrusions / the total particle diameter of the first insulating particles and the average particle diameter of the second insulating particles) is equal to or less than the above upper limit, the insulation reliability and the conduction reliability and The insulation reliability against impact is further increased.

  With respect to the first insulating particles arranged on the surface of the conductive particles so as to be in contact with the conductive particles in the portion where the conductive particles do not have the protrusion, the tip of the first insulating particle is the protrusion of the protrusion. It is preferable to be at a position closer to the center of the conductive particles than the tip. With respect to the second insulating particles disposed on the surface of the first insulating particles so that the conductive particles do not come into contact with the conductive particles, the average height of the protrusions is By being larger than the average particle diameter of one insulating particle, the tip of the second insulating particle is likely to be located farther from the center of the conductive particle than the tip of the protrusion.

  Therefore, if the average height of the protrusion is larger than the average particle diameter of the first insulating particles, and the upper and lower electrodes are electrically connected using the conductive particles with insulating particles, the connection is established. It is possible to suppress electrical connection between electrodes that are adjacent in the lateral direction. That is, insulation reliability can be improved. Normally, during conductive connection, a large force that affects the detachment of the first and second insulating particles is applied. As a result, the first and second insulating particles are detached and exposed conductive particles. Contacts the electrode. Furthermore, if the upper and lower electrodes are electrically connected using the conductive particles with insulating particles, the first and second insulating particles located between the conductive particles and the electrodes are sufficiently eliminated. , The connection resistance is lowered. As a result, conduction reliability between the electrodes can be improved.

  Furthermore, since the average height of the protrusions is larger than the average particle diameter of the first insulating particles, the first insulating particles are not intended from the surface of the conductive particles due to an impact before the conductive connection. It is also possible to effectively prevent detachment. For example, when the conductive particles with insulating particles are dispersed in the binder resin, the first insulating particles can be prevented from being detached from the surface of the conductive particles. Furthermore, when a plurality of conductive particles with insulating particles come into contact with each other, the first insulating particles are hardly detached from the surface of the conductive particles due to an impact at the time of contact. Moreover, even if an impact is applied to the connection structure by electrically connecting the upper and lower electrodes using conductive particles with insulating particles to obtain a connection structure, the first insulating particles are not intended. Since desorption is suppressed, it is possible to suppress electrical connection between adjacent electrodes, and to ensure sufficient insulation reliability. In addition, even if the second insulating particles are detached by impact before the conductive connection, the first insulating particles can be prevented from being detached.

  In order to increase the insulation reliability, it is conceivable to increase the average particle diameter of the insulating particles. However, if only one kind of insulating particles having a large average particle diameter is used, the insulating particles located between the conductive particles and the electrode during the conductive connection are not easily removed, and the insulating property before the conductive connection is obtained. Unintentional detachment of particles tends to occur. On the other hand, in order to increase the detachability of the insulating particles located between the conductive particles and the electrode during the conductive connection, or to suppress the unintentional detachment of the insulating particles before the conductive connection, It is conceivable to reduce the average particle size of the insulating particles. However, when only one type of insulating particles having a small average particle diameter is used, the conductive particles with insulating particles have a tip closer to the center of the conductive particles than a tip of the projection. The insulation reliability tends to be difficult to ensure.

  On the other hand, at least a part of the plurality of second insulating particles is arranged on the surface of the first insulating particles so as not to contact the conductive particles, so that the insulation reliability can be improved. In addition, the conduction reliability can be further improved. In addition, at least a part of the plurality of second insulating particles is arranged on the surface of the first insulating particles so as not to contact the conductive particles, whereby the first and second The insulating part in the whole insulating particle can be made high, and the tip of the insulating part is easily located farther from the center of the conductive particle than the tip of the protrusion. In addition, since the average height of the protrusions is larger than that of the first insulating particles, it becomes difficult for the first insulating particles to be unintentionally detached before the conductive connection, thereby further improving the insulation reliability. it can. Moreover, since the average height of the protrusion is smaller than the sum of the average particle diameter of the first insulating particles and the average particle diameter of the second insulating particles, the insulation reliability can be further improved. In addition, unintentional detachment of the insulating portion before the conductive connection can be suppressed.

  In addition, the first insulating particles disposed on the portions where the conductive particles do not have protrusions and the second insulating particles disposed on the surface of the first insulating particles are the first insulating particles. This contributes to increasing the insulation reliability because the conductive particles are difficult to desorb unintentionally. Note that the first insulating particles disposed on the portions where the conductive particle protrusions are present and the second insulating particles disposed on the surface of the first insulating particles are relatively detached at the time of conductive connection. Cheap. For this reason, it is difficult to be sandwiched between the conductive particles and the electrode after the conductive connection. In addition, since the first insulating particles are also relatively small, they are not easily sandwiched between the conductive particles and the electrode after the conductive connection.

  Furthermore, an oxide film may be formed on the surface of the conductive particles. Further, an oxide film is often formed on the surface of the electrode connected by the conductive particles with insulating particles. When conductive particles with insulating particles having protrusions on the surface of the conductive particles are used, the oxide film can be effectively applied by the protrusions by placing and bonding the conductive particles with insulating particles between the electrodes. Can be eliminated. For this reason, an electrode and an electroconductive part contact more reliably and the connection resistance between electrodes becomes still lower. Furthermore, when the electrodes are connected, the insulating particles between the conductive particles and the electrodes can be effectively eliminated by the protrusions of the conductive particles. For this reason, the conduction | electrical_connection reliability between electrodes becomes still higher.

  The average height of the protrusions indicates an average value of the heights of a plurality of protrusions per conductive particle with insulating particles, and the protrusion height is a line connecting the center of the conductive particles and the tip of the protrusion. On the phantom line (dashed line L2 shown in FIG. 1) of the conductive part on the assumption that there is no projection on the (dashed line L1 shown in FIG. 1) outer surface of the spherical conductive particles on the assumption that there is no projection The distance from the top) to the tip of the protrusion. That is, in FIG. 1, the distance from the intersection of the broken line L1 and the broken line L2 to the tip of the protrusion is shown.

  From the viewpoint of further increasing the insulation reliability, conduction reliability, and insulation reliability against impact, the average particle size of the second insulating particles may be smaller than the average particle size of the first insulating particles. preferable. The average particle size of the second insulating particles is preferably 9/10 or less, more preferably 4/5 or less, and more preferably 2/3 or less of the average particle size of the first insulating particles. More preferably, it is particularly preferably 1/2 or less. The average particle diameter of the second insulating particles is preferably 1/30 or more, more preferably 1/20 or more, and more preferably 1/10 or more of the average particle diameter of the first insulating particles. More preferably.

  The “average particle diameter” of the first and second insulating particles represents a number average particle diameter. The average particle diameter of the first and second insulating particles is determined by observing 50 arbitrary conductive particles with insulating particles with an electron microscope or an optical microscope and calculating an average value.

  From the viewpoint of further improving the conduction reliability, the insulation reliability, and the insulation reliability against impact, the second insulating particles arranged on the surface of the first insulating particles so as not to contact the conductive particles. A larger number is more preferable. It is preferable that 10% or more of the total number of the second insulating particles is arranged on the surface of the first insulating particles so as not to contact the conductive particles. The ratio X1 of the number of the second insulating particles arranged on the surface of the first insulating particles so as not to contact the conductive particles is preferably more than 0%, preferably 10% or more, more preferably Is 20% or more, more preferably 30% or more, particularly preferably 40% or more, and most preferably 50% or more. The total number of second insulating particles indicates the number of second insulating particles that one conductive particle with insulating particles has.

  From the viewpoint of further improving the conduction reliability, the insulation reliability, and the insulation reliability against impact, at least a part of the plurality of second insulating particles is the conductive particle side of the first insulating particles. It is preferably arranged on the opposite surface. That is, it is preferable that the second insulating particles are arranged at a sufficient distance from the conductive particles. The 2nd insulating particle arrange | positioned on the surface on the opposite side to the electroconductive particle side in a 1st insulating particle plays the role which provides cushioning properties, for example. The surface opposite to the conductive particle side of the first insulating particle is the side opposite to the conductive particle side of the first insulating particle when the surface area of the first insulating particle is divided into two equal parts. Refers to the half surface area located at.

  From the viewpoint of further increasing the insulation reliability and the insulation reliability against impact, the second insulation particles are arranged on the surface opposite to the conductive particles side in the first insulation particles. A larger number of second insulating particles is preferable. It is preferable that 5% or more of the total number of the plurality of second insulating particles is disposed on the surface of the first insulating particle opposite to the conductive particle side. The ratio X2 of the number of the second insulating particles arranged on the surface opposite to the conductive particle side in the first insulating particles is more preferably 5% or more, further preferably 10% or more, particularly Preferably it is 15% or more, most preferably 20% or more.

  From the viewpoint of further increasing the insulating property, the second insulating particles in contact with the conductive particles and the conductive portion so as not to contact the first insulating particles among the total number of the second insulating particles. The number ratio X3 is preferably more than 0%, preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more.

  From the viewpoint of further improving the conduction reliability, the insulation reliability, and the insulation reliability against impact, the first insulating particles arranged in the portion without the protrusion of the conductive particles and the portion with the protrusion are arranged. Of the total number of the first insulating particles, the ratio X4 of the first insulating particles arranged in the portion without the projection of the conductive particles is preferably more than 0%, preferably 10% or more, It is preferably 20% or more, preferably 40% or more, more preferably 50% or more, still more preferably 60% or more, and particularly preferably 70% or more. Note that the total number of the first insulating particles arranged in the portions where the conductive particles have no protrusions and the first insulating particles arranged in the portions where the protrusions are present is the conductive particles with insulating particles. The number of the first insulating particles that one particle has is shown.

  From the viewpoint of further improving the conduction reliability, the insulation reliability, and the insulation reliability against impact, the first particles disposed on the surface of the conductive particles per one conductive particle with the insulating particles. The average number Y1 of the insulating particles is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, particularly preferably 5 or more, particularly preferably 10 or more, most preferably 20 or more, preferably Is 100 or less, more preferably 50 or less. The average number Y1 may be less than 20 or 10 or less.

  From the viewpoint of further improving the conduction reliability, the insulation reliability, and the insulation reliability against shock, the first insulating particles arranged on the surface of the first insulating particles per one of the first insulating particles. The average number Y2 of the two insulating particles is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 100 or less, more preferably 50 or less. The average number Y2 may be less than 20 or 10 or less.

  From the viewpoint of further increasing the insulation reliability and the insulation reliability against impact, it is preferable that the second insulating particles adhere to the surface of the first insulating particles through a chemical bond.

  From the viewpoint of further suppressing unintentional detachment of the first insulating particles from the surface of the conductive particles due to the impact, the first particles are bonded to the surface of the conductive particles via a chemical bond. It is preferable that the insulating particles adhere. In addition, when the first insulating particles adhere to the surface of the conductive particles through chemical bonds, the insulation reliability of the connection structure is further increased.

  From the viewpoint of further increasing the insulation reliability, the glass transition temperature (Tg) of the first insulating particles is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 90 ° C. or higher. The upper limit of Tg of the first insulating particles is not particularly limited. From the viewpoint of further increasing the insulation reliability, the glass transition temperature (Tg) of the second insulating particles is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 90 ° C. or higher. The upper limit of Tg of the second insulating particles is not particularly limited.

  Hereinafter, the details of the conductive particles, the first insulating particles, and the second insulating particles in the conductive particles with insulating particles will be described.

[Conductive particles]
The conductive particles are disposed on the surface of the base material particle so as to cover the base material particle, the core material disposed on the surface of the base material particle, and the base material particle and the core material. And a conductive portion.

  Examples of the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. The base particles may be core-shell particles. Especially, it is preferable that the said base particle is a base particle except a metal particle, and it is more preferable that it is an inorganic particle or an organic inorganic hybrid particle except a resin particle, a metal particle. From the viewpoint of further improving the insulation reliability, resin particles are preferable. From the viewpoint of further improving the conduction reliability, organic-inorganic hybrid particles are preferable. From the viewpoint of suppressing an increase in connection resistance in the presence of an acid, resin particles are preferable.

  The substrate particles are preferably resin particles formed of a resin. When connecting the electrodes using the conductive particles with insulating particles, the conductive particles with insulating particles are compressed by placing the conductive particles with insulating particles between the electrodes and then pressing them. When the substrate particles are resin particles, the conductive particles are likely to be deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction | electrical_connection reliability between electrodes becomes still higher.

  Various organic materials are suitably used as the resin for forming the resin particles. 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; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Tons, polyethersulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylenically unsaturated group is polymerized with one or more thereof. Since the hardness of the base particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.

  When the resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having the ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer. And a polymer.

  Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate (Meth) acrylates; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; vinyl acids such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate Esters; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene Is mentioned.

  Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane-containing monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane It is done.

  The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.

  In the case where the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal, examples of the inorganic material for forming the substrate particles include silica and carbon black. Although it does not specifically limit as the particle | grains formed with the said silica, For example, after hydrolyzing the silicon compound which has two or more hydrolysable alkoxysil groups, and forming a crosslinked polymer particle, it calcinates as needed. The particle | grains obtained by performing are mentioned. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

  When the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium. However, the substrate particles are preferably not metal particles.

  The metal for forming the conductive part is not particularly limited. Furthermore, in the case where the conductive particles are metal particles that are conductive parts as a whole, the metal for forming the metal particles is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and these. And the like. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes becomes still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable. The conductive part preferably contains nickel or copper, and more preferably contains nickel. From the viewpoint of suppressing an increase in connection resistance in the presence of an acid, the conductive portion preferably contains nickel. The melting point of the conductive part is preferably 300 ° C. or higher, more preferably 450 ° C. or higher. The conductive part may be a conductive part that is not solder.

  In many cases, hydroxyl groups are present on the surface of the conductive portion by oxidation. In general, a hydroxyl group exists on the surface of a conductive portion formed of nickel by oxidation. The first insulating particles can be attached to the surface of the conductive part having such a hydroxyl group (the surface of the conductive particles) through a chemical bond.

  The conductive layer may be formed of a single layer. The conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked structure of two or more layers. When the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable. When the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced. Moreover, from a viewpoint of improving conduction reliability, the outer surface portion of the conductive portion preferably contains nickel or copper, and more preferably contains nickel. From the viewpoint of suppressing an increase in connection resistance in the presence of an acid, the outer surface portion of the conductive portion preferably contains nickel.

  Since the effect of maintaining the connection resistance low when the connection structure is exposed to the presence of an acid is further obtained, the conductive part (conductive layer) preferably has a nickel conductive part (nickel layer).

  The nickel conductive portion (nickel layer) contains nickel as a main component. In 100% by weight of the nickel conductive part (nickel layer), the content of nickel is 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more. The nickel conductive portion (nickel layer) may contain phosphorus, boron, tungsten, molybdenum and the like. The nickel conductive portion (nickel layer) may contain elements other than these.

  The method for forming the conductive layer on the surface of the substrate particles is not particularly limited. As a method for forming the conductive layer, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc. Especially, since formation of a conductive layer is simple, the method by electroless plating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.

  The average particle diameter of the conductive particles 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, and particularly preferably 20 μm or less. When the average particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrodes is sufficiently large when the electrodes are connected using the conductive particles with insulating particles. And it becomes difficult to form aggregated conductive particles when the conductive layer is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.

  The “average particle size” of the conductive particles indicates a number average particle size. The average particle diameter of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.

  The thickness of the conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 0.3 μm or less. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting the electrodes. .

  When the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is preferably 0.001 μm or more, more preferably the thickness of the gold layer when the outermost layer is a gold layer. It is 0.01 μm or more, preferably 0.5 μm or less, more preferably 0.1 μm or less. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficiently high. Lower. Further, the thinner the gold layer when the outermost layer is a gold layer, the lower the cost.

  The thickness of the conductive layer can be measured, for example, by observing the cross section of the conductive particles or the conductive particles with insulating particles using a transmission electron microscope (TEM).

  As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive layer by electroless plating after attaching a core substance to the surface of the base particles, conductive by electroless plating on the surface of the base particles. Examples include a method of forming a conductive layer by electroless plating after depositing the core material after forming the layer, and a method of depositing the core material in the process of forming the conductive layer on the surface of the substrate particles. . As another method for forming the protrusion, a first conductive layer is formed on the surface of the base particle, and then a core substance is disposed on the first conductive layer, and then the second conductive layer. And a method of adding a core substance in the middle of forming the conductive layer on the surface of the base particle.

  As a method of attaching the core substance to the surface of the base particle, for example, the core substance is added to the dispersion of the base particle, and the core substance is accumulated on the base particle surface by, for example, van der Waals force. And a method of attaching the polymer material to the surface of the base material particles, then attaching the core material by collecting the core material by the electrostatic force, and adding the core material to the container containing the base material particles. And a method of attaching the core substance to the surface of the base particle by a mechanical action such as rotation of the container. Especially, since the quantity of the core substance to adhere is easy to control, the method of making a core substance accumulate and adhere on the surface of the base particle in a dispersion liquid is preferable.

  The conductive particles may have a first conductive layer on the surface of the base particle, and may have a second conductive layer on the first conductive layer. In this case, a core substance may be attached to the surface of the first conductive layer. The core substance is preferably covered with a second conductive layer. The thickness of the first conductive layer is preferably 0.05 μm or more, and preferably 0.5 μm or less. The conductive particles form a first conductive layer on the surface of the base particle, and then a core material is deposited on the surface of the first conductive layer, and then the first conductive layer and the core material are formed. It is preferably obtained by forming a second conductive layer on the surface.

  The material which comprises the said core substance is a metal oxide except an inorganic substance or an inorganic substance. The material constituting the core substance is preferably alumina, tungsten or titania because it is more excellent due to the effects of the present invention.

  The shape of the core material is not particularly limited. The shape of the core substance is preferably a lump. Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.

  The average diameter (average particle diameter) of the core substance is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, more preferably 0.2 μm or less. When the average diameter of the core substance is not less than the above lower limit and not more than the upper limit, the connection resistance between the electrodes is effectively reduced.

  The “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter). The average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.

  The number of the protrusions per conductive particle is preferably 3 or more, more preferably 5 or more. The upper limit of the number of protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.

(First and second insulating particles)
The first and second insulating particles are particles having insulating properties. Each of the first and second insulating particles is smaller than the conductive particles. When the electrodes are connected using conductive particles with insulating particles, the first and second insulating particles can prevent a short circuit between adjacent electrodes. Specifically, when the conductive particles with a plurality of insulating particles come into contact with each other, the first and second insulating particles exist between the conductive particles in the conductive particles with a plurality of insulating particles. It is possible to prevent a short circuit between electrodes adjacent in the horizontal direction, not between the upper and lower electrodes. In addition, when connecting the electrodes, the first and second insulating particles between the conductive portion and the electrode can be easily removed by pressurizing the conductive particles with insulating particles with two electrodes. . Since the protrusion is provided on the surface of the conductive particle, the first and second insulating particles between the conductive portion and the electrode can be more easily eliminated.

  Examples of the material constituting the first and second insulating particles include an insulating resin and an insulating inorganic substance. As said insulating resin, the said resin quoted as resin for forming the resin particle which can be used as a base particle is mentioned. As said insulating inorganic substance, the said inorganic substance quoted as an inorganic substance for forming the inorganic particle which can be used as a base particle is mentioned.

  Specific examples of the insulating resin that is the material of the first and second insulating particles include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, and thermoplastics. Examples include cross-linked resins, thermosetting resins, and water-soluble resins.

  Examples of the polyolefins include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate. 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. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. 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, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.

  From the viewpoint of further enhancing the detachability of the first and second insulating particles during the pressure bonding, each of the first and second insulating particles is preferably an inorganic particle, and is preferably a silica particle. It is preferable.

  Examples of the inorganic particles include shirasu particles, hydroxyapatite particles, magnesia particles, zirconium oxide particles, and silica particles. Examples of the silica particles include pulverized silica and spherical silica. Spherical silica is preferably used. The silica particles preferably have a functional group capable of chemical bonding such as a carboxyl group and a hydroxyl group on the surface, and more preferably have a hydroxyl group. Inorganic particles are relatively hard, especially silica particles are relatively hard. When the conductive particles with insulating particles including such hard insulating particles are used, when the conductive particles with insulating particles and the binder resin are kneaded, the surface of the conductive particles has a hard insulating property. There is a tendency for particles to be easily detached. On the other hand, when the conductive particles with insulating particles according to the present invention are used, even if the hard first insulating particles are used, the second insulating particles are used during the kneading. It is possible to suppress the separation of one insulating particle. The second insulating particles play a role of imparting cushioning properties, for example.

  It is preferable that the second insulating particles adhere to the surface of the first insulating particles through a chemical bond. It is preferable that the first insulating particles are attached to the surface of the conductive particles through a chemical bond. This chemical bond includes a covalent bond, a hydrogen bond, an ionic bond, a coordination bond, and the like. Among these, a covalent bond is preferable, and a chemical bond using a reactive functional group is preferable.

  Examples of the reactive functional group that forms the chemical bond include a vinyl group, (meth) acryloyl group, silane group, silanol group, carboxyl group, amino group, ammonium group, nitro group, hydroxyl group, carbonyl group, thiol group, Examples thereof include a sulfonic acid group, a sulfonium group, a boric acid group, an oxazoline group, a pyrrolidone group, a phosphoric acid group, and a nitrile group. Among these, a vinyl group and a (meth) acryloyl group are preferable.

  From the viewpoint of further suppressing the detachment of the first insulating particles and further improving the insulation reliability in the connection structure, the insulating particles having a reactive functional group on the surface as the first insulating particles. Is preferably used. From the viewpoint of further suppressing the detachment of the insulating particles and further improving the insulation reliability in the connection structure, the first insulating particles were subjected to a surface treatment using a compound having a reactive functional group. It is preferable to use the first insulating particles. Further, from the viewpoint of further increasing the insulation reliability, it is preferable to use insulating particles having reactive functional groups on the surface as the second insulating particles. From the viewpoint of further increasing the insulation reliability, it is preferable to use second insulating particles that have been surface-treated using a compound having a reactive functional group as the second insulating particles.

  Examples of the reactive functional group that can be introduced on the surfaces of the first and second insulating particles include a (meth) acryloyl group, a glycidyl group, a hydroxyl group, a vinyl group, and an amino group. The reactive functional group on the surface of the first and second insulating particles is at least one kind of reactivity selected from the group consisting of (meth) acryloyl group, glycidyl group, hydroxyl group, vinyl group and amino group. It is preferably a functional group.

  Examples of the compound (surface treatment substance) for introducing the reactive functional group include a compound having a (meth) acryloyl group, a compound having an epoxy group, a compound having a vinyl group, and the like.

  Examples of the compound (surface treatment substance) for introducing a vinyl group include a silane compound having a vinyl group, a titanium compound having a vinyl group, and a phosphate compound having a vinyl group. The surface treatment substance is preferably a silane compound having a vinyl group. Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and vinyltriisopropoxysilane.

  As a compound (surface treatment substance) for introducing a (meth) acryloyl group, a silane compound having a (meth) acryloyl group, a titanium compound having a (meth) acryloyl group, and a phosphoric acid having a (meth) acryloyl group Compounds and the like. The surface treatment substance is also preferably a silane compound having a (meth) acryloyl group. Examples of the silane compound having a (meth) acryloyl group include (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltridimethoxysilane, and the like.

  As a method of attaching the first insulating particles to the surface of the conductive particles and the conductive part and a method of attaching the second insulating particles to the surface of the first insulating particles, a chemical method and a physical Or mechanical methods. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include a spray drying method, a hybridization method, an electrostatic adhesion method, a spray method, a dipping method, and a vacuum deposition method. However, since the hybridization method tends to cause the detachment of the insulating particles, the method of arranging the first and second insulating particles is preferably a method other than the hybridization method. It is preferable that the first insulating particles are not arranged on the surface of the conductive particles by the hybridization method. The second insulating particles are preferably not arranged on the surface of the first insulating particles by the hybridization method. Since the first insulating particles are more difficult to be detached, a method of arranging the first insulating particles on the surface of the conductive particles through a chemical bond is preferable.

  The following method is mentioned as an example of the method of attaching the 1st, 2nd insulating particle to the surface of the said electroconductive particle, and the surface of the said electroconductive part.

  First, the conductive particles are put in 3 L of a solvent such as water, and the first and second insulating particles are gradually added while stirring. In addition, after the second insulating particles are attached in advance to the surface of the first insulating particles, the conductive particles are put in 3 L of a solvent such as water, and the second insulating particles are attached while stirring. The first insulating particles may be gradually added. After sufficiently stirring, the conductive particles with insulating particles are separated and dried by a vacuum dryer or the like to obtain conductive particles with insulating particles.

  It is preferable that the conductive part has a reactive functional group capable of reacting with the first insulating particles on the surface. The first insulating particles preferably have a reactive functional group capable of reacting with the conductive part on the surface. By introducing a chemical bond with these reactive functional groups, it becomes difficult for the first insulating particles to be unintentionally detached from the surface of the conductive particles. In addition, the insulation reliability and the insulation reliability against impact are further enhanced.

  The surface of the conductive part and the surface of the first insulating particle may be coated with a compound having a reactive functional group. The surface of the conductive part and the surface of the first insulating particles may not be directly chemically bonded, and may be indirectly chemically bonded by a compound having a reactive functional group.

  After introducing a carboxyl group into the surface of the conductive part, the carboxyl group may be chemically bonded to a functional group on the surface of the insulating particle through a polymer electrolyte such as polyethyleneimine.

  As the reactive functional group, an appropriate group is selected in consideration of reactivity. Examples of the reactive functional group include a hydroxyl group, a vinyl group, and an amino group. Since the reactivity is excellent, the reactive functional group is preferably a hydroxyl group. The conductive particles preferably have a hydroxyl group on the surface. The conductive part preferably has a hydroxyl group on the surface. The insulating particles preferably have a hydroxyl group on the surface.

  When there are hydroxyl groups on the surface of the insulating particles and the surface of the conductive particles, the adhesion between the first insulating particles and the conductive particles is moderately increased by the dehydration reaction.

  Examples of the compound having a hydroxyl group include a P—OH group-containing compound and a Si—OH group-containing compound. Examples of the compound having a hydroxyl group for introducing a hydroxyl group on the surface of the insulating particles include a P—OH group-containing compound and a Si—OH group-containing compound.

  Specific examples of the P-OH group-containing compound include acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and acid phosphooxypolyoxypropylene glycol monomethacrylate. As for the said P-OH group containing compound, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the Si-OH group-containing compound include vinyltrihydroxysilane and 3-methacryloxypropyltrihydroxysilane. As for the said Si-OH group containing compound, only 1 type may be used and 2 or more types may be used together.

  For example, insulating particles having a hydroxyl group on the surface can be obtained by a treatment using a silane coupling agent. Examples of the silane coupling agent include hydroxytrimethoxysilane.

(Conductive material)
The conductive material according to the present invention includes the conductive particles with insulating particles according to the present invention and a binder resin. When the conductive particles with insulating particles according to the present invention are dispersed in the binder resin, the first and second insulating particles are hardly detached from the surface of the conductive particles. The conductive particles with insulating particles according to the present invention are preferably dispersed in a binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material.

  The binder resin is not particularly limited. In general, an insulating resin is used as the binder resin. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder resin, only 1 type may be used and 2 or more types may be used together.

  Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin. Examples of the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated product of a styrene block copolymer. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

  In addition to the conductive particles with insulating particles and the binder resin, the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, and heat stability. Various additives such as an agent, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.

  The method for dispersing the conductive particles with insulating particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used. Examples of a method for dispersing conductive particles with insulating particles in a binder resin include, for example, a method in which conductive particles with insulating particles are added to a binder resin and then kneaded and dispersed with a planetary mixer or the like. Conductive particles with particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, then added to the binder resin, kneaded and dispersed with a planetary mixer, etc., and the binder resin is water or organic Examples include a method of adding conductive particles with insulating particles after diluting with a solvent or the like, and kneading and dispersing with a planetary mixer or the like.

  The conductive material according to the present invention can be used as a conductive paste and a conductive film. When the conductive material according to the present invention is a conductive film, a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

  The conductive material according to the present invention is preferably a conductive paste. The conductive paste is excellent in handleability and circuit fillability. Although a relatively large force is applied to the conductive particles with insulating particles when obtaining the conductive paste, the insulating particles are detached from the surface of the conductive particles due to the presence of the second insulating particles. Can be suppressed.

  In 100% by weight of the conductive material, the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles with insulating particles are efficiently arranged between the electrodes, and the conduction reliability of the connection target member connected by the conductive material is further increased. Get higher.

  The content of the conductive particles with insulating particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60%. % By weight or less, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 15% by weight or less. When the content of the conductive particles with insulating particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.

(Connection structure)
By using the conductive particles with insulating particles described above, or by using a conductive material including the conductive particles with insulating particles and a binder resin, a connection structure can be obtained by connecting the connection target members. it can.

  The connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection portion. Is formed of the conductive particles with insulating particles described above, or a connection structure formed of a conductive material (such as an anisotropic conductive material) containing the conductive particles with insulating particles and a binder resin. Preferably there is. The first connection target member preferably has a first electrode on the surface. The second connection object member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles. When the conductive particles with insulating particles described above are used, the connection portion itself is formed of conductive particles with insulating particles. That is, the first and second connection target members are electrically connected by the conductive particles in the conductive particles with insulating particles.

  FIG. 6 is a cross-sectional view schematically showing a connection structure using the conductive particles 1 with insulating particles shown in FIG.

  A connection structure 81 shown in FIG. 6 includes a first connection target member 82, a second connection target member 83, and a connection that connects the first connection target member 82 and the second connection target member 83. Part 84. The connecting portion 84 is formed of a conductive material including the conductive particles 1 with insulating particles and a binder resin. In FIG. 6, the conductive particles 1 with insulating particles are schematically shown for convenience of illustration. Instead of the conductive particles 1 with insulating particles, conductive particles 1A, 1B, 1C, and 1D with insulating particles may be used.

  The first connection target member 82 has a plurality of first electrodes 82a on the surface (upper surface). The second connection target member 83 has a plurality of second electrodes 83a on the surface (lower surface). The 1st electrode 82a and the 2nd electrode 83a are electrically connected by the electroconductive particle 2 in the electroconductive particle 1 with one or some insulating particle. Therefore, the first and second connection target members 82 and 83 are electrically connected by the conductive particles 1 with insulating particles.

The manufacturing method of the connection structure is not particularly limited. As an example of a method of manufacturing a connection structure, a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc. The pressure of the said pressurization is about 9.8 * 10 < ⁴ > -4.9 * 10 < ⁶ > Pa. The temperature of the said heating is about 120-220 degreeC.

  When the laminate is heated and pressurized, the first and second insulating particles 3 and 4 existing between the conductive particles 2 and the first and second electrodes 82a and 83a can be eliminated. For example, during the heating and pressurization, the first and second insulating particles 3 and 4 existing between the conductive particles 2 and the first and second electrodes 82a and 83a are melted. Or the surface of the conductive particles 2 is partially exposed. It should be noted that since a large force is applied during the heating and pressurization, some of the first and second insulating particles 3 and 4 are detached from the surface of the conductive particles 2 and the conductive particles. The surface of 2 may be partially exposed. The portion where the surface of the conductive particle 2 is exposed contacts the first and second electrodes 82a and 83a, so that the first and second electrodes 82a and 83a are electrically connected through the conductive particle 2. it can.

  Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. The conductive material is in a paste form, and is preferably applied on the connection target member in a paste state. The conductive particles with insulating particles and the conductive material are preferably used for connection of a connection target member that is an electronic component. The connection target member is preferably an electronic component. The conductive particles with insulating particles are preferably used for electrical connection of electrodes in an electronic component.

  The conductive particles with insulating particles according to the present invention are particularly suitable for COG having a glass substrate and a semiconductor chip as connection target members, or FOG having a glass substrate and a flexible printed circuit board (FPC) as connection target members. Is done. The conductive particles with insulating particles according to the present invention may be used for COG or FOG. In the connection structure according to the present invention, the first and second connection target members are preferably a glass substrate and a semiconductor chip, or a glass substrate and a flexible printed board. The first and second connection target members may be a glass substrate and a semiconductor chip, or may be a glass substrate and a flexible printed board.

It is preferable that bumps are provided on a semiconductor chip used in a COG having a glass substrate and a semiconductor chip as connection target members. The bump size is preferably an electrode area of 1000 μm ² or more and 10,000 μm ² or less. The electrode space in the semiconductor chip provided with the bump (electrode) is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. For such COG applications, the conductive particles with insulating particles according to the present invention are preferably used. In the FPC used in the FOG using a glass substrate and a flexible printed circuit as a connection target member, the electrode space is preferably 30 μm or less, more preferably 20 μm or less.

  Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode. When the connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably 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 with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

  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
(Electroless plating pretreatment process)
About 10 g of resin particles (average particle size 3 μm) formed from a copolymer resin of tetramethylolmethanetetraacrylate and divinylbenzene, alkali degreasing with sodium hydroxide aqueous solution, acid neutralization, and sensitizing in tin dichloride solution are performed. It was.

  The resin particles were treated with an ion adsorbent for 5 minutes and then added to an aqueous palladium sulfate solution. Thereafter, dimethylamine borane was added for reduction treatment, filtration, and washing to obtain resin particles to which palladium was attached.

(Core material compounding process)
10 g of resin particles provided with a palladium catalyst were dispersed in 300 mL of ion-exchanged water to prepare a dispersion. 1 g of metallic nickel particles (average particle size 50 nm) was added to the dispersion over 3 minutes to prepare resin particles to which the metallic nickel particles adhered.

(Electroless nickel plating process)
Next, a 1% by weight sodium succinate solution in which sodium succinate was dissolved in 500 mL of ion exchange water was prepared. 10 g of resin particles having alumina particles and palladium attached thereto were added to this solution and mixed to prepare a slurry. Sulfuric acid was added to the slurry, and the pH of the slurry was adjusted to 5.

  As a nickel plating solution, a nickel plating solution containing 10% by weight of nickel sulfate, 10% by weight of sodium hypophosphite, 4% by weight of sodium hydroxide and 20% by weight of sodium succinate was prepared. The slurry adjusted to pH 5 was heated to 80 ° C., and then the nickel plating solution was continuously added dropwise to the slurry and stirred for 20 minutes to advance the plating reaction. After confirming that hydrogen was no longer generated, the plating reaction was completed.

  Next, a late nickel plating solution containing 20% by weight of nickel sulfate, 5% by weight of dimethylamine borane and 5% by weight of sodium hydroxide was prepared. The late nickel plating solution was continuously added dropwise to the solution after the plating reaction with the previous nickel plating solution, and the plating reaction was allowed to proceed by stirring for 1 hour. In this way, a nickel layer was formed on the surface of the resin particles, and conductive particles A were obtained. The nickel layer had a thickness of 0.1 μm.

(Process for producing insulating particles)
A 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a condenser tube, and a temperature probe, glycidyl methacrylate 45 mmol, methyl methacrylate 380 mmol, dimethacrylate ethylene glycol 13 mmol, acid phosphooxypolyoxyethylene A monomer composition containing 0.5 mmol of glycol methacrylate and 1 mmol of 2,2′-azobis {2- [N- (2-carboxyethyl) amidino] propane} was added. Distilled water was added to the monomer composition so that the solid content was 10% by weight, and the mixture was stirred at 150 rpm and polymerized at 60 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was freeze-dried to obtain first insulating particles (average particle diameter 300 nm) having P—OH groups derived from acid phosphooxypolyoxyethylene glycol methacrylate on the surface. The Tg of the first insulating particles was 100 ° C.

  Moreover, the 2nd insulating particle (average particle diameter of 100 nm) was obtained by the same method except having changed said stirring speed into 300 rpm and superposition | polymerization temperature to 80 degreeC. The Tg of the second insulating particles was 100 ° C.

(Process for producing conductive particles with insulating particles)
The insulating particles obtained above were each dispersed in distilled water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles. 10 g of the obtained conductive particles A were dispersed in 500 mL of distilled water, a mixed solution of 4 g of the first insulating particle aqueous dispersion and 2 g of the second insulating particle aqueous dispersion was added, and the mixture was stirred at room temperature for 8 hours. Stir. After filtration through a 3 μm mesh filter, the product was further washed with methanol and dried to obtain conductive particles with insulating particles.

  When observed with a scanning electron microscope (SEM), the conductive particles with insulating particles had a coating layer of insulating particles formed on the surface of the conductive particles having protrusions.

(Examples 2 to 9, Reference Examples 10 and 11 and Comparative Example 2)
The material of the core substance was set as shown in Table 1 below, the average height of the protrusion was set as shown in Table 1 below according to the average particle diameter of the core substance, and the first and second insulating properties The average particle diameter of the particles was set as shown in Table 1 below, and addition of aqueous dispersions of the first and second insulating particles to change the presence state of the first and second insulating particles Example 1 except that the amount was controlled
In the same manner, conductive particles with insulating particles were obtained.

(Example 12)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that conductive particles were produced using resin particles having an average particle size of 2.0 μm.

(Example 13)
Organic-inorganic hybrid particles (average) formed from resin particles (average particle size 3 μm) formed from a copolymer resin of tetramethylolmethanetetraacrylate and divinylbenzene and divinylbenzene and a copolymer of siloxane having a vinyl group Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the particle diameter was changed to 3 μm.

(Example 14)
Resin particles (average particle size 3 μm) formed from a copolymer resin of tetramethylolmethane tetraacrylate and divinylbenzene have vinyl groups on the core resin particles of divinylbenzene copolymer having a particle size of 2.5 μm. Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the organic inorganic core-shell particles were formed with a siloxane copolymer shell (thickness: 0.25 μm).

(Example 15)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the copper plating solution was used instead of the nickel plating solution to obtain conductive particles having a copper layer formed on the surface of the resin particles. It was. The copper layer had a thickness of 0.1 μm.

(Example 16)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that methyl methacrylate was changed to styrene in the production steps of the first and second insulating particles. The Tg of the first insulating particles was 80 ° C. The Tg of the second insulating particles was 80 ° C.

(Comparative Example 1)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the core material was not combined in the conductive particle production step.

(Comparative Example 3)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that 0.5 mmol of hexadecyltrimethylammonium bromide (CTAB) was added in the insulating particle manufacturing step.

(Evaluation)
(1) Of the total number of second insulating particles, the ratio X1 of the number of second insulating particles arranged on the surface of the first insulating particles so as not to contact the conductive particles
In the obtained conductive particles with insulating particles, the second insulation arranged on the surface of the first insulating particles so as not to contact the conductive particles out of the total number of the second insulating particles. The ratio X1 (%) of the number of the functional particles was determined. The number ratio X1 was determined according to the following criteria.

  The surface of 20 conductive particles with insulating particles was photographed by SEM, and the first insulating particles and the second insulating particles coated on the surface of the conductive particles were counted.

[Criteria of the ratio X1 of the number of second insulating particles arranged on the surface of the first insulating particles so as not to contact the conductive particles out of the total number of second insulating particles]
A: Number ratio X1 is 30% or more B: Number ratio X1 is 10% or more and less than 30% C: Number ratio X1 exceeds 0% and less than 10% D: Number ratio X1 is 0%

(2) Of the total number of second insulating particles, the ratio X2 of the number of second insulating particles arranged on the surface of the first insulating particles opposite to the conductive particles side
In the obtained conductive particles with insulating particles, the second insulation disposed on the surface of the first insulating particles opposite to the conductive particles in the total number of the second insulating particles. The ratio X2 (%) of the number of the functional particles was determined. The number ratio X2 was determined according to the following criteria.

[Judgment criteria for the ratio X2 of the number of second insulating particles arranged on the surface of the first insulating particles opposite to the conductive particles in the total number of second insulating particles]
A: Number ratio X2 is 20% or more B: Number ratio X2 is 5% or more and less than 20% C: Number ratio X2 is less than 5%

(3) Of the total number of second insulating particles, the ratio X3 of the number of second insulating particles arranged on the surface of the conductive particles so as not to contact the first insulating particles
In the obtained conductive particles with insulating particles, the second insulating material disposed on the surface of the conductive particles so as not to contact the first insulating particles out of the total number of the second insulating particles. The ratio X3 (%) of the number of particles was determined. The number ratio X3 was determined according to the following criteria.

[Criteria of the ratio X3 of the number of second insulating particles arranged on the surface of the conductive particles so as not to contact the first insulating particles among the total number of the second insulating particles]
A: Number ratio X3 is 15% or more B: Number ratio X3 is 10% or more and less than 15% C: Number ratio X3 exceeds 0% and less than 10% D: Number ratio X3 is 0%

(4) Of the total number of the first insulating particles disposed in the portion without the protrusion of the conductive particles and the first insulating particles disposed in the portion with the protrusion, the protrusion of the conductive particle Ratio X4 of the first insulating particles arranged in a portion where there is no particle
In the obtained conductive particles with insulating particles, all of the first insulating particles arranged in the portions without the protrusions of the conductive particles and the first insulating particles arranged in the portions with the protrusions. The ratio X4 (%) of the 1st insulating particle arrange | positioned in the part which does not have the protrusion of electroconductive particle among the number was calculated | required. The number ratio X4 was determined according to the following criteria.

[No projection of conductive particles out of the total number of the first insulating particles arranged in the portion without the projection of the conductive particles and the first insulating particles arranged in the portion of the projection. Criteria for the ratio X4 of the first insulating particles arranged in the portion]
A: Number ratio X4 is 20% or more B: Number ratio X4 is 10% or more and less than 20% C: Number ratio X4 is more than 0% and less than 10% D: Number ratio X4 is 0%

(5) Average number Y1 of the first insulating particles arranged on the surface of the conductive particles per one conductive particle with insulating particles
In the obtained conductive particles with insulating particles, the average number Y1 of the first insulating particles arranged on the surface of the conductive particles per one conductive particle with insulating particles was determined. The average number Y1 was determined according to the following criteria.

[Judgment Criteria for Average Number Y1 of First Insulating Particles Disposed on the Surface of Conductive Particles per Conductive Particle with Insulating Particles]
A: Average number Y1 is 20 or more and 100 or less B: Average number Y1 is 3 or more and less than 20 C: Average number Y1 is less than 3

(6) The average number Y2 of second insulating particles arranged on the surface of the first insulating particles per first insulating particle
In the obtained conductive particles with insulating particles, the average number Y2 of the second insulating particles arranged on the surface of the first insulating particles per one first insulating particle was determined. . The average number Y2 was determined according to the following criteria.

[Judgment Criteria for Average Number Y2 of Second Insulating Particles Disposed on the Surface of First Insulating Particles per First Insulating Particle]
A: Average number Y2 is 20 or more and 100 or less B: Average number Y2 is 3 or more and less than 20 C: Average number Y2 is less than 3

(7) Conduction reliability (between upper and lower electrodes)
20 parts by weight of an epoxy compound which is a thermosetting compound (“EP-3300P” manufactured by ADEKA), 15 parts by weight of an epoxy compound which is a thermosetting compound (“EPICLON HP-4032D” manufactured by DIC), and a thermosetting agent 5 parts by weight of a thermal cation generator (manufactured by Sanshin Chemical Co., Ltd., Sun Aid “SI-60”) and 20 parts by weight of silica (average particle diameter: 0.25 μm) as a filler were further blended, and the insulation obtained After adding conductive particles with conductive particles so that the content in 100% by weight of the formulation is 10% by weight, the anisotropic conductive paste is obtained by stirring at 2000 rpm for 5 minutes using a planetary stirrer. Obtained.

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

  On the transparent glass substrate, the obtained anisotropic conductive paste was applied to a thickness of 30 μm to form an anisotropic conductive paste layer. Next, the semiconductor chip was stacked on the anisotropic conductive paste layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 1 MPa is applied to form the anisotropic conductive paste layer. It hardened | cured at 185 degreeC and the connection structure was obtained.

  The connection resistances A between the upper and lower electrodes of the 20 obtained connection structures were measured by the four-terminal method. Note that the connection resistance can be obtained by measuring the voltage when a constant current is passed from the relationship of voltage = current × resistance. The conduction reliability was determined according to the following criteria.

[Judgment criteria for conduction reliability]
○○: The ratio of the number of connection structures having a connection resistance A of 5Ω or less is 80% or more. ○: The ratio of the number of connection structures having a connection resistance A of 5Ω or less is 65% or more and less than 80%. The ratio of the number of connection structures having a resistance of 5Ω or less is 50% or more and less than 65%.

(8) Insulation reliability (between adjacent electrodes in the horizontal direction)
In the 20 connection structures obtained in the above (7) evaluation of conduction reliability, the presence or absence of leakage between adjacent electrodes was evaluated by measuring resistance with a tester. Insulation reliability was judged according to the following criteria.

[Criteria for insulation reliability]
○○: Ratio of the number of connection structures having a resistance value of 10 ⁸ Ω or more is 80% or more ○: Ratio of the number of connection structures having a resistance value of 10 ⁸ Ω or more is 65% or more and less than 80% Δ: Resistance The ratio of the number of connection structures having a value of 10 ⁸ Ω or more is 50% or more and less than 65% ×: The ratio of the number of connection structures having a resistance value of 10 ⁸ Ω or more is less than 50%

(9) Connection resistance after being exposed to the presence of acid The connection structure obtained by the above (7) evaluation of conduction reliability was left in a constant temperature and humidity chamber at 85 ° C. and a humidity of 85% for 100 hours. By leaving the connection structure under the above conditions, the connection part between the electrodes in the connection structure is exposed for a certain period in the presence of acid due to the reaction between the water infiltrated into the binder resin and the acid contained in the binder resin. It was. In the connection structure after being left, the connection resistance B between the opposing electrodes of the connection structure was measured by a four-terminal method. Moreover, the connection resistance after being exposed to the presence of an acid was determined according to the following criteria.

[Evaluation criteria for connection resistance after exposure to acid]
◯: Connection resistance B is less than 1 time of connection resistance A ○: Connection resistance B is 1 time or more and less than 1.5 times of connection resistance A △: Connection resistance B is 1.5 times or more of connection resistance A 2 Less than x: Connection resistance B is more than twice connection resistance A

  The results are shown in Table 1 below.

1, 1A, 1B, 1C, 1D ... conductive particles with insulating particles 2, 2C ... conductive particles 2a, 2Ca ... projections 3, 3A, 3D ... first insulating particles 4, 4A, 4D ... second Insulating particles 11 ... base particle 12, 12C ... conductive part 12CA ... first conductive part 12CB ... second conductive part 13 ... core substance 81 ... connection structure 82 ... first connection target member 82a ... first Electrode 83 ... 2nd connection object member 83a ... 2nd electrode 84 ... Connection part

Claims (9)

Conductive particles;
A plurality of first insulating particles disposed on the surface of the conductive particles so as to contact the surface of the conductive particles;
A plurality of second insulating particles,
The conductive particles are disposed on the surface of the base material particle so as to cover the base material particle, the core material disposed on the surface of the base material particle, and the base material particle and the core material. And a conductive part
The conductive substance has a plurality of protrusions on the surface by causing the outer surface of the conductive portion to protrude from the core substance,
The average height of the protrusions is smaller than the sum of the average particle diameter of the first insulating particles and the average particle diameter of the second insulating particles,
The ratio of the average height of the protrusions to the average particle diameter of the first insulating particles is 1.1 or more,
At least some of the plurality of second insulating particles are disposed on the surface of the first insulating particles so as not to contact the conductive particles;
Conductive particles with insulating particles, wherein the material of the core substance is a metal oxide or tungsten carbide excluding inorganic substances.   The conductive particles with insulating particles according to claim 1, wherein the material of the core substance is alumina, tungsten carbide, or titania.   The conductive particles with insulating particles according to claim 1 or 2, wherein an average particle size of the second insulating particles is smaller than an average particle size of the first insulating particles. More than 10% of the total number of the second insulating particles, so as not to contact the conductive particles, the first are arranged on the surface of the insulating particles, according to claim 1 to 3 The electroconductive particle with an insulating particle of any one of Claims 1. On the surface of the first insulating particles, through chemical bonds, said second insulating particles are adhered, insulating particles with the conductive particles according to any one of claims 1-4 . Wherein the surface of the conductive particles, through chemical bonds, said first insulating particles are adhered, insulating particles with the conductive particles according to any one of claims 1-5. The first insulating particles are not arranged on the surface of the conductive particles by a hybridization method,
The conductive particles with insulating particles according to any one of claims 1 to 6 , wherein the second insulating particles are not arranged on the surface of the first insulating particles by a hybridization method. . And insulating particles with conductive particle according to any one of claims 1 to 7 and a binder resin, conductive material. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
The first connection target member, and a connection portion connecting the second connection target member,
The connection part is formed of the conductive particles with insulating particles according to any one of claims 1 to 7 , or formed of a conductive material including the conductive particles with insulating particles and a binder resin. Has been
The connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles.

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