JP2015005499A - Conductive particle with insulative particles, conductive material and connection structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive particle with insulative particles capable of enhancing conduction reliability and insulation reliability after conductive connection.SOLUTION: There is provided a conductive particle 1 with insulative particles which comprises: a conductive particle 2 having a conductive part 12 at least on the surface thereof; a plurality of insulative particles 3 disposed on the surface of the conductive particle 2; and an insulative layer 4 which covers the surface of a part where insulative particles 3 of the conductive particle 2 are not disposed, wherein the insulative layer 4 is formed by polymerization of a polymerizable compound, the conductive part 12 and the insulative particles 3 are chemically bonded and the conductive part 12 and the insulative layer 4 are chemically bonded.

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 particles, the following Patent Document 1 discloses conductive with insulating particles having conductive particles and insulating particles fixed to the surface of the conductive particles and having adhesive properties. Particles are disclosed. The insulating particles include hard particles and a polymer resin layer covering the surfaces of the hard particles. Here, a physical / mechanical hybridization method is used as an immobilization method in order to immobilize the insulating particles on the surface of the conductive particles.

  Patent Document 2 below includes conductive particles having a polar group on at least a part of a surface, and an insulating material that covers at least a part of the surface of the conductive particles and includes insulating particles. A conductive particle with insulating particles is disclosed. Specifically, the insulating material includes a polymer electrolyte that can adsorb the polar group, and inorganic oxide particles that can adsorb the polymer electrolyte. The inorganic oxide particles are insulating particles.

  Patent Document 3 below discloses conductive particles with insulating particles in which an insulating layer is formed on the surface of a conductive core having a conductive surface, and the insulating particles are embedded in the insulating layer. Has been. Patent Document 3 describes in claim 5 that “insulating fine particles are embedded in an insulating layer of a conductive core having an insulating layer formed on the surface of the core by hybridization treatment”, paragraph [0033] Describes that “the embedding of the insulating fine particles 32 can be performed by a known hybridization process”.

  The following Patent Document 4 discloses conductive particles with insulating particles in which insulating particles having a particle diameter equal to or smaller than the particle diameter of the conductive particles are attached to the surface of the conductive particles. In Patent Document 4, the third page of the specification, upper left column, line 17 to upper right column, line 1 “As a method for attaching insulating particles to the surface of conductive particles, for example, conductive particles and insulating particles are used in a container. In other words, a well-known method such as a method of adhering due to the difference in the polarity of charging caused by friction is adopted.

  In the following Patent Document 5, conductive particles with conductive particles are attached to the surface of the conductive particles. The conductive particles are smaller than the conductive particles and have insulating particles that are harder than the adhesive under the connecting conditions. Particles are disclosed. The conductive particles are particles obtained by substantially covering a core material made of a polymer with a thin conductive metal layer. In Patent Document 5, in the paragraph [0021] of the specification, “as a method of immobilizing the insulating particles 3 on the heat-deformable conductive particles 5, for example, a granulation method such as a spray method or a high-speed stirring method is applicable. As a manufacturing apparatus by such a method, it is commercially available under trade names such as Mechanomyl (Okada Seiko), Ongmill (Hosokawa Micron), Hybridization System (Nara Machinery), Coat Mizer (Freund Sangyo), Klux System (Orient Chemical). Both are preferably applicable. ”

Special table 2007-537570 gazette JP 2008-120990 A JP 2005-209491 A Japanese Patent Laid-Open No. 3-112011 JP-A-4-259766

  In recent years, there has been a demand for reducing the power consumption of electronic devices and reducing the pitch of circuit wiring. For this reason, for example, for conductive particles with insulating particles used for the connection between the upper and lower electrodes, the connection resistance is lowered after the connection between the upper and lower electrodes, and the insulation reliability between the lateral electrodes is increased. Is required.

  However, in the conventional conductive particles with insulating particles as described in Patent Documents 1 to 5, the connection resistance between the upper and lower electrodes is increased, and the insulation reliability between the lateral electrodes is decreased. In other words, the conventional conductive particles with insulating particles have a problem that it is difficult to improve both the conduction reliability and the insulation reliability.

  Moreover, in the conventional conductive particles with insulating particles as described in Patent Documents 1 and 2, the insulating particles are easily detached from the surface of the conductive particles unintentionally before the conductive connection. For example, when the conductive particles with insulating particles are dispersed in the binder resin, the insulating particles may be easily detached from the surface of the conductive particles.

  In particular, as described in Patent Document 1, when a physical / mechanical hybridization method is used to immobilize the insulating particles on the surface of the conductive particles, the insulating particles are made of conductive particles. Easily detached from the surface.

  Moreover, in the conductive particles with insulating particles obtained by the methods described in Patent Documents 3 to 5, the insulating particles are likely to be unintentionally detached from the surface of the conductive particles before the conductive connection, Sometimes the insulating particles are not easily detached from the surface of the conductive particles. When the conductive particles are not easily detached from the surface of the conductive particles during the conductive connection, the insulating particles may be sandwiched between the conductive particles and the electrode, or the conductive particles and the electrode may not be in contact with each other. . If the conductive particles do not contact the electrode, poor connection occurs.

  The objective of this invention is providing the electroconductive particle with an insulating particle which can improve both conduction | electrical_connection reliability and insulation reliability after electroconductive connection.

  The limited object of the present invention is that the insulating particles are not easily detached from the surface of the conductive particles unintentionally before the conductive connection, and the insulating particles are easily detached from the surface of the conductive particles during the conductive connection. It is to provide conductive particles with insulating particles.

  Another object of the present invention is 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, conductive particles having a conductive portion on at least a surface thereof, a plurality of insulating particles disposed on the surface of the conductive particles, and the insulating particles of the conductive particles are disposed. An insulating layer covering the surface of the portion that is not formed, the insulating layer is formed by polymerizing a polymerizable compound, and the conductive portion and the insulating particles are chemically In addition, conductive particles with insulating particles, which are bonded to each other and are chemically bonded to the conductive portion and the insulating layer, are provided.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the insulating particles and the insulating layer have a portion in contact with each other, and the insulating property is in the contacted portion. The particles and the insulating layer are chemically bonded.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the insulating layer covers a surface of a portion of the conductive particles where the insulating particles are not disposed. And a second portion covering the surface of the insulating particles.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the first portion and the second portion are continuous.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, the first portion of the insulating layer covering the surface of the conductive particles where the insulating particles are not disposed. The average thickness is 1/2 or less of the average particle diameter of the insulating particles.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, 90% or more of the total number of the plurality of insulating particles is in contact with the conductive particles.

  In a specific aspect of the conductive particles with insulating particles according to the present invention, a plurality of the insulating particles are not exposed by being covered with the insulating layer.

  On the specific situation with the electroconductive particle with an insulating particle which concerns on this invention, the said electroconductive particle has several protrusion on the surface of the said electroconductive part.

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

  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 conductive particles with insulating particles described above, or the conductive particles with insulating particles and a binder. A connection structure, wherein the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles. The body is provided.

  The conductive particles with insulating particles according to the present invention include conductive particles having at least a conductive portion on a surface thereof, a plurality of insulating particles disposed on the surface of the conductive particles, and the insulation of the conductive particles. An insulating layer covering the surface of the portion where the conductive particles are not disposed, and further, the insulating layer is formed by polymerizing a polymerizable compound, and the conductive portion and the insulating layer are formed. Since the conductive particles are chemically bonded, and the conductive portion and the insulating layer are chemically bonded, both conductive reliability and insulating reliability are obtained after the conductive connection. Can be increased.

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 front cross-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)
The conductive particles with insulating particles according to the present invention include conductive particles having at least a conductive portion on a surface thereof, a plurality of insulating particles disposed on the surface of the conductive particles, and the insulation of the conductive particles. And an insulating layer covering the surface of the portion where the conductive particles are not disposed. In the conductive particles with insulating particles according to the present invention, the insulating layer is formed by polymerizing a polymerizable compound. In the conductive particles with insulating particles according to the present invention, the conductive part and the insulating particle are chemically bonded, and the conductive part and the insulating layer are chemically bonded. ing. The insulating layer covers at least the surface of the conductive particles where the insulating particles are not disposed.

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

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

  The conductive particle 2 includes a base particle 11 and a conductive portion 12 disposed on the surface of the base particle 11. The electroconductive particle 2 has the electroconductive part 12 on the surface. 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 plurality of insulating particles 3 are disposed on the surface of the conductive particles 2. The plurality of insulating particles 3 are attached to the surface of the conductive particles 2. The insulating particles 3 are made of an insulating material.

  The insulating layer 4 is formed by polymerizing a polymerizable compound. The conductive portion 12 and the insulating particles 3 are chemically bonded. Furthermore, the conductive part 12 and the insulating layer 4 are chemically bonded. The insulating layer 4 includes a first portion 4 a that covers the surface of the portion of the conductive particle 2 where the insulating particles 3 are not disposed, and a second portion that covers the surface of the insulating particle 3. 4b.

  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 a conductive particle 2A having a core substance 13, a plurality of insulating particles 3, and an insulating layer 4A. The conductive particles 2A have a conductive portion 12A on the surface. The plurality of insulating particles 3 are arranged on the surface of the conductive particles 2A. 4 A of insulating layers have coat | covered the surface of the part by which the insulating particle 3 of the electroconductive particle 2A is not arrange | positioned.

  The conductive particle 2 </ b> A includes the base particle 11 and a conductive portion 12 </ b> A disposed on the surface of the base particle 11. The conductive portion 12A is a conductive layer. The conductive particle 2 </ b> A has a plurality of core substances 13 on the surface of the base particle 11. The conductive portion 12 </ b> A covers the base particle 11 and the core substance 13. By covering the core substance 13 with the conductive portion 12A, the conductive particles 2A have a plurality of protrusions 2Aa on the surface of the conductive portion 12A. The surface of the conductive portion 12A is raised by the core substance 13, and a plurality of protrusions 2Aa are formed. By forming the protrusion 2Aa, the conductive particles 2A, the conductive part 12A and the insulating layer 4A are different from the conductive particles 2, the conductive part 12 and the insulating layer 4 in accordance with the shape of the protrusion 2Aa. .

  The insulating layer 4A is formed by polymerizing a polymerizable compound. The conductive portion 12A and the insulating particles 3 are chemically bonded. Further, the conductive portion 12A and the insulating layer 4A are chemically bonded. 4 A of insulating layers have coat | covered the surface of the part by which the insulating particle 3 of the electroconductive particle 2A is not arrange | positioned. The insulating layer 4 </ b> A includes a first portion 4 </ b> Aa that covers the surface of the conductive particle 2 </ b> A where the insulating particles 3 are not disposed, and a second portion that covers the surface of the insulating particle 3. 4 Ab.

  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 1B with insulating particles shown in FIG. 3 includes a conductive particle 2B having a core substance 13, a plurality of insulating particles 3, and an insulating layer 4B.

  The conductive particle 2 </ b> B includes base material particles 11 and a conductive portion 12 </ b> B disposed on the surface of the base material particles 11. The conductive part 12B is a conductive layer. The conductive particle 2 </ b> B has a plurality of core substances 13 on the surface of the base particle 11. The conductive part 12 </ b> B covers the base particle 11 and the core substance 13. By covering the core substance 13 with the conductive portion 12B, the conductive particles 2B have a plurality of protrusions 2Ba on the surface of the conductive portion 12B. The surface of the conductive portion 12B is raised by the core substance 13, and a plurality of protrusions 2Ba are formed.

  The conductive part 12B includes a first conductive part 12BA disposed on the surface of the base particle 11 and a second conductive part 12BB disposed on the surface of the first conductive part 12BA. The first and second conductive portions 12BA and 12BB are conductive layers.

  The conductive particle 2B has a plurality of core substances 13 disposed on the surface of the first conductive portion 12BA. The second conductive portion 12BB covers the first conductive portion 12BA and the core substance 13. The substrate particles 11 and the core substance 13 are arranged with a space therebetween. A first conductive portion 12BA exists between the base particle 11 and the core substance 13. By covering the core substance 13 with the second conductive portion 12BB, the conductive particles 2B have a plurality of protrusions 2Ba on the surface of the second conductive portion 12BB. The surface of the second conductive portion 12BB is raised by the core substance 13, and a plurality of protrusions 2Ba are formed.

  The insulating layer 4B is formed by polymerizing a polymerizable compound. The conductive portion 12B and the insulating particles 3 are chemically bonded. Furthermore, the conductive portion 12B and the insulating layer 4B are chemically bonded. The insulating layer 4B covers the surface of the portion of the conductive particles 2B where the insulating particles 3 are not disposed. The insulating layer 4B includes a first portion 4Ba covering the surface of the conductive particles 2B where the insulating particles 3 are not disposed, and a second portion covering the surface of the insulating particles 3. 4Bb.

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

  A conductive particle 1C with insulating particles shown in FIG. 4 includes a conductive particle 2A having a core substance 13, a plurality of insulating particles 3, and an insulating layer 4C.

  The insulating layer 4C is formed by polymerizing a polymerizable compound. In the conductive particles 1C with insulating particles, the conductive portion 12A and the insulating particles 3 are chemically bonded. Furthermore, the conductive portion 12A and the insulating layer 4C are chemically bonded. The insulating layer 4C covers the surface of the portion of the conductive particles 2A where the insulating particles 3 are not disposed. The insulating layer 4C has a first portion 4Ca that covers the surface of the portion of the conductive particle 2A where the insulating particles 3 are not disposed, but the second portion that covers the surface of the insulating particles 3. There is no part.

  In the conductive particles with insulating particles 1, 1A, 1B, and 1C, the insulating particles 3 and the insulating layers 4, 4A, 4B, and 4C have portions in contact with each other. In this contacting portion, the insulating particles 3 and the insulating layers 4, 4A, 4B, 4C are chemically bonded. Thus, from the viewpoint of further improving the insulation reliability, it is preferable that the insulating particles and the insulating layer are chemically bonded. Since the insulating particles and the insulating layer are chemically bonded, the insulation reliability is sufficiently ensured even when the pitch between the electrodes is narrow.

  In the conductive particles 1, 1 </ b> A, 1 </ b> B with insulating particles, the insulating layers 4, 4 </ b> A, 4 </ b> B cover the surface of the conductive particles 2, 2 </ b> A, 2 </ b> B where the insulating particles 3 are not disposed. It has 1st part 4a, 4Aa, 4Ba and 2nd part 4b, 4Ab, 4Bb which coat | covers the surface of the insulating particle 3. As shown in FIG. As described above, from the viewpoint of further increasing the insulation reliability, the insulating layer includes a first portion covering a surface of a portion of the conductive particles where the insulating particles are not disposed, It is preferable to have the said 2nd part which coat | covers the surface of an insulating particle. Since the insulating layer has the first portion and the second portion, insulation reliability is sufficiently ensured even when the pitch between the electrodes is narrow.

  The average thickness of the first portion covering the surface of the conductive particles in the insulating layer where the insulating particles are not disposed is ½ or less of the average particle diameter of the insulating particles. It is preferable that In this case, before the conductive connection, the insulating particles are less likely to be detached from the surface of the conductive particles unintentionally, and during the conductive connection, the insulating particles are further detached from the surface of the conductive particles. It becomes easy. Therefore, when the electrodes are connected using the conductive particles with insulating particles, the conduction reliability is further enhanced. That is, in the conductive particles with insulating particles, both the anti-detachment property before the conductive connection of the insulating particles and the release property during the conductive connection are enhanced. In general, a larger force that affects the detachment of insulating particles is applied during conductive connection than before conductive connection.

  From the viewpoint of effectively suppressing the separation of the insulating particles from the surface of the conductive particles during the conductive connection, the surface of the portion of the insulating layer where the insulating particles are not disposed in the insulating layer The thinner the average thickness of the first part covering the film, the better. The average thickness of the first portion covering the surface of the conductive particles in the insulating layer where the insulating particles are not disposed is 1/3 or less of the average particle diameter of the insulating particles. More preferably, it is more preferably 1/5 or less. In order to effectively perform the function of preventing the detachment before the conductive connection of the insulating particles, the surface of the insulating layer where the insulating particles of the conductive particles are not disposed is coated. The average thickness of the first portion is preferably 1/100 or more of the average particle diameter of the insulating particles, and more preferably 1/20 or more.

  The “average particle diameter” of the insulating particles indicates a number average particle diameter. 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 average thickness of the first portion that covers the surface of the conductive particle in the insulating layer where the insulating particle is not disposed is the first thickness that covers the surface of the insulating particle. The part 2 may be the same or different. The thickness of the first portion is preferably 5 nm or more, more preferably 20 nm or more, preferably 150 nm or less, more preferably 80 nm or less. The thickness of the second portion is preferably 10 nm or more, more preferably 40 nm or more, preferably 300 nm μm or less, more preferably 150 nm or less.

  From the viewpoint of further improving the insulation reliability after the conductive connection, and effectively preventing unintentional detachment of the insulating particles from the surface of the conductive particles before the conductive connection. It is preferable that 50% or more of the total number of the plurality of insulating particles in the conductive particles is in contact with the conductive particles. 90% or more of the total number of the plurality of insulating particles in the conductive particles with insulating particles is more preferably in contact with the conductive particles, and 95% or more is in contact with the conductive particles. More preferably.

  From the viewpoint of further improving the insulation reliability after the conductive connection, and effectively preventing unintentional detachment of the insulating particles from the surface of the conductive particles before the conductive connection, the first part It is preferable that the second portion is continuous.

  From the viewpoint of further improving the insulation reliability after the conductive connection, and effectively preventing unintentional detachment of the insulating particles from the surface of the conductive particles before the conductive connection, a plurality of the above insulating properties It is preferable that the particles are not exposed by being covered with the insulating layer. It is preferable that the conductive particles with insulating particles do not have insulating particles that are not covered with the insulating layer and exposed.

  Moreover, when the said insulating layer coat | covers the surface of the part in which the said insulating particle of the said electroconductive particle is not arrange | positioned, it becomes difficult to produce rust in the electroconductive part in the electroconductive particle with an insulating particle. The insulating layer imparts a rust prevention effect. For this reason, the electroconductivity of the electroconductive particle in the electroconductive particle with an insulating particle becomes high, and can maintain high electroconductivity over a long period of time. Therefore, when the electrodes are connected using conductive particles with insulating particles, the conduction reliability can be improved.

  Moreover, it is preferable that the said insulating layer is formed with the high molecular compound containing the compound which has a C6-C22 alkyl group. Thereby, it becomes difficult to produce rust in the electroconductive part in the electroconductive particle with an insulating particle.

  From the viewpoint of further increasing the insulation reliability, it is preferable that the conductive portion is not exposed by being covered with the insulating layer.

  In addition, the said insulating layer may coat | cover only the one part area | region of the said electroconductive part, and may coat | cover the said electroconductive part so that the one part area | region of the said electroconductive part may be exposed. Even if the insulating layer covers the conductive portion so that a part of the conductive portion is exposed, the insulating layer is formed by the presence of the portion covered by the insulating layer. Compared with the case where there is no covered portion, the insulation reliability is further increased.

  The conductive particles with insulating particles may be obtained through a step of forming an insulating layer so that the insulating particles cover the surface of the conductive particles arranged on the surface of the conductive part.

  Hereinafter, details of the insulating layer, conductive particles, insulating particles, and the like will be described.

[Insulating layer]
The insulating layer is formed by polymerizing a polymerizable compound. The polymerizable compound is preferably a radical polymerizable compound. In this case, a radical polymerization initiator is generally used to form an insulating layer. The insulating layer is made of a compound having two or more alkyl groups having 6 to 22 carbon atoms and a reactive functional group (hereinafter, also referred to as compound A) in order to make it difficult for rust to occur in the conductive part. Is preferred. The compound A is a polymerizable compound. When the carbon number of the alkyl group is less than 6, rust is likely to occur on the surface of the conductive portion. When carbon number of the said alkyl group exceeds 22, the electroconductivity of the electroconductive particle with an insulating particle will become low. From the viewpoint of further increasing the conductivity of the conductive particles with insulating particles, the alkyl group in the compound A preferably has 16 or less carbon atoms. The alkyl group may have a linear structure or a branched structure. The alkyl group preferably has a linear structure.

  It is preferable that at least one of the two or more reactive functional groups is a functional group capable of reacting with the conductive particles and the conductive part. Due to the presence of the reactive functional group, it is easy to chemically bond the conductive particles and the insulating layer, or to chemically bond the insulating particles and the insulating layer. Unintentional peeling of the insulating layer is less likely to occur due to the chemical bond, rust is less likely to occur in the conductive portion, and the insulating particles are more unintentionally detached from the surface of the conductive particles.

  At least one of the two or more reactive functional groups is preferably a functional group that can be polymerized with the polymerizable monomer. The presence of the reactive functional group makes it easy to control the insulating layer by a polymerization reaction. As a result, rust is less likely to occur in the conductive portion.

  The compound A is not particularly limited as long as it has two or more alkyl groups having 6 to 22 carbon atoms and reactive functional groups.

  The compound A is preferably at least one selected from the group consisting of a phosphate ester or a salt thereof, a phosphite ester or a salt thereof, an alkoxysilane, an alkylthiol, and a dialkyl disulfide. By using these preferable compounds A, it is possible to further prevent rust from being generated in the conductive portion. From the viewpoint of making rust more difficult to occur, the compound A is preferably at least one selected from the group consisting of the phosphate ester or a salt thereof, a phosphite ester or a salt thereof and an alkoxysilane, More preferably, the phosphoric acid ester or a salt thereof and a phosphorous acid ester or a salt thereof are at least one of them. As for the said compound A, only 1 type may be used and 2 or more types may be used together.

  The compound A preferably has a reactive functional group capable of reacting with the conductive particles and the conductive part. The compound A preferably has a reactive functional group capable of reacting with insulating particles. Due to the presence of the reactive functional group, it is easy to chemically bond the conductive particles and the insulating layer, or to chemically bond the insulating particles and the insulating layer. Unintentional peeling of the insulating layer is less likely to occur due to the chemical bond, rust is less likely to occur in the conductive portion, and the insulating particles are more unintentionally detached from the surface of the conductive particles.

  At least one of the two or more reactive functional groups is preferably at least one selected from a vinyl group, a (meth) acryloyl group, a carboxyl group, and a polymerizable reactive group. Examples of the polymerizable reactive group include polymerizable reactive groups such as an unsaturated hydrocarbon group. By polymerizing monomers having these reactive functional groups and ethylenically unsaturated groups, the insulating layer can be easily controlled. The insulating layer formed by this polymerization reaction makes it more difficult for rust to occur in the conductive portion.

  Examples of the compound having two or more alkyl groups having 6 to 22 carbon atoms and two or more reactive functional groups include, for example, phosphate hexenyl ester, phosphate heptynyl ester, phosphate monooctynyl ester, phosphate monononiel ester, Examples thereof include monodecynyl phosphate, oleyl phosphate, and vinyl phosphate.

  As a compound which polymerizes with the reactive functional group mentioned above, the compound similar to resin for forming base particle can be used. Examples of the compound include styrene, (meth) acrylic acid, methyl (meth) acrylate, and glycidyl methacrylate.

  After chemically bonding at least one of the reactive functional groups to the surface of the conductive particles, the other reactive functional groups are polymerized with the polymerizable monomer by a known method to form the surface of the conductive particles. An insulating layer can be formed.

  At this time, the polymerizable monomer may be chemically bonded to a reactive functional group present on the surface of the insulating particles. The polymerizable monomer may be chemically bonded to both the compound derived from the compound A formed on the surface of the conductive particle and the reactive functional group on the surface of the insulating particle.

[Conductive particles]
The said electroconductive particle should just have an electroconductive part on the surface at least. The conductive part is, for example, a conductive layer. The conductive particles may be conductive particles having base particles and conductive portions arranged on the surface of the base particles, or may be conductive particles (metal particles) whose entirety is a conductive portion. Good. Among these, from the viewpoint of reducing the cost and increasing the flexibility of the conductive particles to increase the conduction reliability between the electrodes, the base particles and the conductive material disposed on the surface of the base particles are used. The electroconductive particle which has a part is preferable.

  Examples of the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. The substrate particles are preferably substrate particles excluding metal particles, and are preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles. The organic-inorganic hybrid particles may have a core and a shell disposed on the surface of the core.

  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, polypropylene, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate. Polyalkylene 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, poly Chromatography ether ether ketone, polyether sulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylenically unsaturated group is polymerized with one or more thereof. Resin for forming the resin particles can be designed and synthesized, and the hardness of the base particles can be easily controlled within a suitable range, which is suitable for conductive materials and having physical properties at the time of compression. Is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of ethylenically unsaturated groups.

  When the resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. And so on.

  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 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 particles, examples of the inorganic material for forming the substrate particles include silica and carbon black. This inorganic substance is preferably not a metal. The particles formed by the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. 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 tungsten. , Molybdenum, and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes can be made still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.

  As the metal constituting the conductive part is more likely to be rusted, the coating effect by the coating is more remarkable. In the conductive part formed of nickel, copper or tin, rust is relatively easily generated on the surface of the conductive part. By covering the surface of such a conductive part with a film, it is possible to effectively suppress the occurrence of rust on the surface of the conductive part. Since the covering effect by the said film is acquired effectively, the said electroconductive part may contain nickel, copper, or tin.

  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 conductive portion having such a hydroxyl group is chemically bonded to the insulating layer.

  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 can be further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced.

  The method for forming the conductive portion on the surface of the particle is not particularly limited. Examples of the method for forming the conductive part include a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of particles with metal powder or a paste containing metal powder and a binder. Can be mentioned. Especially, since formation of an electroconductive part 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 100 μm or less, more 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. It becomes large and it becomes difficult to form the agglomerated conductive particles when the conductive part is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive portion is difficult to peel from the surface of the base particle.

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

  When the conductive part 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 said electroconductive part can be measured by observing the cross section of electroconductive particle or electroconductive particle with an insulating particle using a transmission electron microscope (TEM), for example.

  The conductive particles preferably have protrusions on the surface of the conductive part, and the protrusions are preferably plural. 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 part are used, the oxide film can be effectively eliminated by the protrusions by disposing the conductive particles between the electrodes and pressing them. For this reason, an electrode and an electroconductive part are contacted still 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 are effectively excluded by the protrusions of the conductive particles. For this reason, the conduction | electrical_connection reliability between electrodes becomes still higher.

  As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive portion by electroless plating after attaching a core substance to the surface of the base particle, conductive by electroless plating on the surface of the base particle. A method of forming a conductive part by forming a conductive material by electroless plating, and a method of forming a conductive part by adding a core material in the middle of forming the conductive part by electroless plating Etc. Note that the core substance is not necessarily used to form the protrusions.

  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 material 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.

  Examples of the material constituting the core material include conductive materials and non-conductive materials. Examples of the conductive material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene. Examples of the nonconductive material include silica, alumina, and zirconia. Among them, metal is preferable because conductivity can be increased. The core substance is preferably metal particles.

  Examples of the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, tungsten, molybdenum, and cadmium. And alloys composed of two or more kinds of metals such as a tin-lead alloy, a tin-copper alloy, a tin-silver alloy, a tin-lead-silver alloy, and tungsten carbide. Of these, nickel, copper, silver or gold is preferable. The metal constituting the core substance may be the same as or different from the metal constituting the conductive part (conductive layer).

  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 height of the plurality of protrusions on the surface of the conductive part 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 height of the protrusions is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes is effectively reduced. From the viewpoint of further increasing the insulation reliability after the conductive connection, it is preferable that the average particle diameter of the insulating particles is larger than the average height of the protrusions.

  The height of the projection is a virtual line of the conductive portion (dashed line shown in FIG. 2) on the assumption that there is no projection on the line connecting the center of the conductive particles and the tip of the projection (dashed line L1 shown in FIG. 2). L2) Indicates the distance from the top (on the outer surface of the spherical conductive particles assuming no projection) to the tip of the projection. That is, in FIG. 2, the distance from the intersection of the broken line L1 and the broken line L2 to the tip of the protrusion is shown.

[Insulating particles]
The insulating particles are particles having insulating properties. Insulating particles are smaller than conductive particles. When the electrodes are connected using conductive particles with insulating particles, the insulating particles can prevent a short circuit between adjacent electrodes. Specifically, when the conductive particles with a plurality of insulating particles are in contact with each other, there are insulating particles between the conductive particles in the conductive particles with a plurality of insulating particles. Short circuit between the electrodes adjacent in the lateral direction can be prevented. In addition, the insulating particle between an electroconductive part and an electrode can be easily excluded by pressurizing the electroconductive particle with an insulating particle with two electrodes in the case of the connection between electrodes. When the conductive particles have protrusions on the conductive surface, the insulating particles between the conductive portion and the electrode can be more easily eliminated.

  Examples of the material constituting the 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 insulating particles include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, heat Examples thereof include curable 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 improving the detachability of the insulating particles during thermocompression bonding, the insulating particles preferably include inorganic particles, and are preferably silica particles. Examples of the inorganic particles include shirasu particles, hydroxyapatite particles, magnesia particles, zirconium oxide particles, and silica particles. From the viewpoint of further improving the detachability of the insulating particles during thermocompression bonding, the insulating particles preferably include silica particles, and the inorganic particles are preferably silica particles. Examples of the silica particles include pulverized silica and spherical silica, and 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 conductive particles with insulating particles having such hard insulating particles are used, when the conductive particles with insulating particles and the binder resin are kneaded, hard insulating properties are obtained from the surface of the conductive particles. Particles are easily detached. However, when the conductive particles with insulating particles according to the present invention are used, even if hard insulating particles are used, the hard insulating particles are detached by the insulating layer during the kneading. Can be suppressed. The insulating layer serves as a flexible layer, for example.

  Examples of the method for attaching insulating particles to the surfaces of the conductive particles and the conductive part include chemical methods and 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 spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. In the present invention, in order to improve both the conduction reliability and the insulation reliability after the conductive connection, the conductive portion and the insulating layer are chemically bonded. In contrast, the hybridization method tends to cause desorption of insulating particles.

  In the conductive particles with insulating particles according to the present invention, the insulating particles are preferably not attached to the surface of the conductive particles by a hybridization method.

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

  The following method is mentioned as an example of the method of making an insulating particle adhere to the surface of the said electroconductive particle and the said electroconductive part.

  First, the conductive particles are put in 3 L of a solvent such as water, and the insulating particles are gradually added while stirring. 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.

  The conductive part preferably has a reactive functional group capable of reacting with the insulating particles on the surface, and preferably has a reactive functional group capable of reacting with the insulating layer. The insulating particles preferably have a reactive functional group capable of reacting with the conductive portion on the surface, and preferably have a reactive functional group capable of reacting with the insulating layer. The insulating layer preferably has a reactive functional group capable of reacting with the conductive portion on the surface, and preferably has a functional group capable of reacting with the insulating particles. By these reactive functional groups, the insulation reliability after the conductive connection is further increased, and further, the insulating particles are difficult to be removed from the surface of the conductive particles unintentionally. The insulating layer is difficult to peel off from the surface of the particles. Furthermore, the surface of the conductive portion can be sufficiently covered with the insulating layer, and the surface of the insulating particles can be sufficiently covered with the insulating layer.

  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 with insulating particles preferably have a hydroxyl group in at least a part of the surface. The conductive particles preferably have a hydroxyl group on the surface. The insulating particles preferably have a hydroxyl group on the surface. The insulating layer preferably has 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 force between the insulating particles and the conductive particles is appropriately 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 and a binder resin. The conductive particles are preferably dispersed in a binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive material is preferably used for electrical connection of electrodes. The conductive material is preferably a circuit connection material.

  When the conductive particles with insulating particles are used, since the surfaces of the insulating particles and the conductive particles are covered with an insulating layer, the conductive portion and the insulating particles are chemically separated. Since they are bonded, it is difficult for the insulating particles to be detached from the surface of the conductive particles when the conductive particles with insulating particles are dispersed in the binder resin.

  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 conductive material according to the present invention can be used as a conductive paste or a conductive film. When the conductive material according to the present invention is used as a conductive film, a film not including conductive particles may be laminated on the conductive film including the 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, and more preferably an anisotropic conductive paste. Conductive pastes such as anisotropic conductive pastes are excellent in handleability and circuit fillability. When a conductive paste is obtained, a relatively large force is applied to the conductive particles with insulating particles, but the presence of the insulating layer can prevent the insulating particles from being detached from the surface of the conductive particles.

  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 are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.

  In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 40% by weight or less, more preferably 20% by weight or less, More preferably, it is 10 weight% or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.

(Connection structure)
A connection structure can be obtained by connecting the connection target members using the conductive particles with insulating particles or using a conductive material containing the conductive particles with insulating particles and a binder resin. .

  The connection structure includes 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 electrode, and the second electrode. A conductive material comprising: a connecting portion electrically connecting the conductive portion with the insulating particles; or a conductive material comprising the conductive particles with insulating particles and a binder resin. A connection structure formed of an anisotropic conductive material or the like is preferable. 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 are used, the connection portion itself is formed by the conductive particles with insulating particles. That is, the first and second electrodes are electrically connected by the conductive particles in the conductive particles with insulating particles.

  FIG. 5 is a cross-sectional view schematically showing a connection structure using the conductive particles 1 with insulating particles shown in FIG.

  The connection structure 51 shown in FIG. 5 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 connecting the first and second connection target members 52 and 53. Prepare. The connection part 54 is formed of a conductive material including the conductive particles 1 with insulating particles and a binder resin. In FIG. 5, for convenience of illustration, the conductive particles 1 with insulating particles are schematically shown. Instead of the conductive particles 1 with insulating particles, conductive particles 1A, 1B, 1C with insulating particles may be used.

  The first connection object member 52 has a plurality of first electrodes 52a on the surface. The second connection target member 53 has a plurality of second electrodes 53a on the surface. The 1st electrode 52a and the 2nd electrode 53a are electrically connected by the electroconductive particle 2 in the electroconductive particle 1 with one or some insulating particle. The first and second connection target members 52 and 53 are connected by components derived from the binder resin contained in the conductive material.

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 pressurization is about 9.8 × 10 ^{4 to} 4.9 × 10 ⁶ Pa. The temperature of the said heating is about 120-220 degreeC.

  When the laminated body is heated and pressurized, the insulating particles existing between the conductive particles and the first and second electricity can be eliminated. For example, during the heating and pressurization, the insulating particles existing between the conductive particles and the first and second electrodes are melted or deformed, so that the conductive The surface of the conductive particles is partially exposed. In addition, since a large force is applied during the heating and pressurization, some of the insulating particles are peeled off from the surface of the conductive particles, and the surface of the conductive particles is partially exposed. Sometimes. The portion where the surface of the conductive particles is exposed contacts the first and second electrodes, whereby the first and second electrodes can be electrically connected via the conductive particles.

  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.

  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
(1) Preparation step of conductive particles Prepare conductive particles (average particle diameter 3.01 μm, conductive layer thickness 0.10 μm) in which a nickel plating layer (conductive layer) is formed on the surface of divinylbenzene resin particles did.

(2) Production process of insulating particles In 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, 380 mmol of methyl methacrylate, 13 mmol of ethylene glycol dimethacrylate, acid phospho A monomer composition containing 0.5 mmol of oxypolyoxyethylene glycol methacrylate and 1 mmol of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] 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 300 rpm and polymerized at 70 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was freeze-dried to obtain insulating particles a (average particle diameter of 300 nm) having the P—OH group derived from acid phosphooxypolyoxyethylene glycol methacrylate on the surface.

  The obtained insulating particles a were dispersed in distilled water to obtain a 10 wt% dispersion of insulating particles a.

(3) Step of producing conductive particles with insulating particles before forming the insulating layer 50 parts by weight of the prepared conductive particles were dispersed in 300 mL of distilled water. To the dispersion, 50 mL of a 10 wt% dispersion of insulating particles a was added dropwise and stirred at 50 ° C. for 8 hours. The dispersion was filtered, washed with methanol, and vacuum dried at 120 ° C. for 7 hours. In this way, by chemically bonding the hydroxyl groups on the surface of the nickel conductive layer and the P—OH groups in the insulating particles, the insulating particles are attached to the surface of the conductive particles, and the insulating layer is formed before the formation. Conductive particles with insulating particles were obtained.

(4) Formation process of insulating layer Oleyl phosphoric acid was dissolved in a solution containing ethanol and pure water at a weight ratio of 1: 1 to obtain a 1% by weight solution of oleyl phosphoric acid. 50 parts by weight of the conductive particles with insulating particles before formation of the obtained insulating layer were placed in 300 mL of a 1% by weight oleyl phosphoric acid solution and stirred at 50 ° C. for 1 hour to obtain a stirring solution. Thereafter, 0.5 parts by weight of methyl methacrylate (MMA, polymerizable compound) and 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] (Wako Pure Chemical) which is a radical polymerization initiator 0.1 part by weight of “VA-057” manufactured by Kogyo Co., Ltd. was put into the solution and stirred at 60 ° C. for 5 hours. As a result, the hydroxyl group on the surface of the nickel conductive layer is chemically bonded to the P—OH group in oleyl phosphate, and the unsaturated bond of oleyl phosphate and the acryloyl group of MMA are chemically bonded to form an insulating layer derived from MMA. The formed conductive particles with insulating particles were obtained.

  In the obtained conductive particles with insulating particles, the insulating layer covers the first part covering the surface of the conductive particles where the insulating particles are not disposed, and the surface of the insulating particles. The first portion and the second portion are connected to each other. The plurality of the insulating particles were not exposed by being covered with the insulating layer. The average thickness of the first part covering the surface of the part where the insulating particles of the conductive particles are not disposed was 100 nm. All of the insulating particles were in contact with the conductive particles.

(Example 2)
(1) Preparation step of conductive particles Prepare conductive particles (average particle diameter 3.01 μm, conductive layer thickness 0.10 μm) in which a nickel plating layer (conductive layer) is formed on the surface of divinylbenzene resin particles did.

(2) Production process of 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 was charged with 45 mmol of glycidyl methacrylate, 380 mmol of methyl methacrylate, and ethylene dimethacrylate. A monomer composition containing 13 mmol of glycol, 0.5 mmol of acid phosphooxypolyoxyethylene glycol methacrylate, and 1 mmol of 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] 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 300 rpm and polymerized at 70 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, freeze-drying is performed to obtain insulating particles b (average particle size of 300 nm) having the above-mentioned P—OH group derived from acid phosphooxypolyoxyethylene glycol methacrylate and the epoxy group derived from glycidyl methacrylate on the surface. It was.

  The obtained insulating particles b were dispersed in distilled water to obtain a 10 wt% dispersion of insulating particles b.

(3) Step of producing conductive particles with insulating particles before forming the insulating layer 50 parts by weight of the prepared conductive particles were dispersed in 300 mL of distilled water. 50 mL of a 10 wt% dispersion of insulating particles b was added dropwise to the dispersion and stirred at 50 ° C. for 8 hours. The dispersion was filtered, washed with methanol, and vacuum dried at 120 ° C. for 7 hours. In this way, the insulating particles are adhered to the surface of the conductive particles by chemically bonding the hydroxyl groups on the nickel metal surface of the conductive particles and the P-OH groups in the insulating particles, thereby forming an insulating layer. The previous conductive particles with insulating particles were obtained.

(4) Formation process of insulating layer Oleyl phosphoric acid was dissolved in a solution containing ethanol and pure water at a weight ratio of 1: 1 to obtain a 1% by weight solution of oleyl phosphoric acid. 50 parts by weight of the conductive particles with insulating particles before formation of the obtained insulating layer were placed in 300 mL of a 1% by weight oleyl phosphoric acid solution and stirred at 50 ° C. for 1 hour to obtain a stirring solution. Thereafter, 0.5 parts by weight of methyl methacrylate (MMA, polymerizable compound), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] (Wako Pure Chemical Industries, Ltd.) which is a radical polymerization initiator "VA-057" manufactured by the company) 0.05 parts by weight, glycidyl methacrylate (polymerizable compound) 0.3 parts by weight, and cationic polymerization initiator ("Sun Aid SI-60" manufactured by Sanshin Chemical Co., Ltd.) 0.05 parts by weight Was added to the solution and stirred at 60 ° C. for 8 hours. As a result, the hydroxyl group on the surface of the nickel conductive layer of the conductive particles is chemically bonded to the P-OH group in oleyl phosphate, and the unsaturated bond of oleyl phosphate and the acryloyl group of MMA and glycidyl methacrylate are chemically bonded to each other. The epoxy group and the epoxy group of the insulating particles were chemically bonded to obtain conductive particles with insulating particles in which an insulating layer derived from MMA and glycidyl methacrylate was formed.

Example 3
Conductive particles in which a nickel core material is attached on the surface of the divinylbenzene resin particles, and a nickel plating layer (conductive layer) is formed on the surface of the divinylbenzene resin particles so as to cover the nickel core material. (Average particle diameter 3.01 μm, conductive layer thickness 0.10 μm, protrusion average height 150 nm) was prepared.

  Except having used the said electroconductive particle, it carried out similarly to Example 1, and obtained the electroconductive particle with an insulating particle.

Example 4
In the same manner as in Example 1, conductive particles with insulating particles before the formation of the insulating layer were obtained.

(4) Formation process of insulating layer Oleyl phosphoric acid was dissolved in a solution containing ethanol and pure water at a weight ratio of 1: 1 to obtain a 1% by weight solution of oleyl phosphoric acid. 50 parts by weight of the conductive particles with insulating particles before formation of the obtained insulating layer were placed in 300 mL of a 1% by weight oleyl phosphoric acid solution and stirred at 50 ° C. for 1 hour to obtain a stirring solution. Thereafter, 1.0 part by weight of methyl methacrylate (MMA, polymerizable compound) and 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] (Wako Pure Chemical) which is a radical polymerization initiator 0.2 part by weight of “VA-057” manufactured by Kogyo Co., Ltd. was put in the solution, and stirred at 60 ° C. for 5 hours. As a result, the hydroxyl group on the surface of the nickel conductive layer is chemically bonded to the P—OH group in oleyl phosphate, and the unsaturated bond of oleyl phosphate and the acryloyl group of MMA are chemically bonded to form an insulating layer derived from MMA. The formed conductive particles with insulating particles were obtained.

  In the obtained conductive particles with insulating particles, the insulating layer covers the first part covering the surface of the conductive particles where the insulating particles are not disposed, and the surface of the insulating particles. The first portion and the second portion are connected to each other. The plurality of the insulating particles were not exposed by being covered with the insulating layer. The average thickness of the first part covering the surface of the part where the insulating particles of the conductive particles are not disposed was 200 nm. All of the insulating particles were in contact with the conductive particles.

(Example 5)
In the same manner as in Example 1, conductive particles with insulating particles before the formation of the insulating layer were obtained.

(4) Formation process of insulating layer Oleyl phosphoric acid was dissolved in a solution containing ethanol and pure water at a weight ratio of 1: 1 to obtain a 1% by weight solution of oleyl phosphoric acid. 50 parts by weight of the conductive particles with insulating particles before formation of the obtained insulating layer were placed in 300 mL of a 1% by weight oleyl phosphoric acid solution and stirred at 50 ° C. for 1 hour to obtain a stirring solution. Thereafter, 0.2 parts by weight of methyl methacrylate (MMA, polymerizable compound) and 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] (Wako Pure Chemical) which is a radical polymerization initiator 0.1 part by weight of “VA-057” manufactured by Kogyo Co., Ltd. was put into the solution and stirred at 60 ° C. for 5 hours. As a result, the hydroxyl group on the surface of the nickel conductive layer is chemically bonded to the P—OH group in oleyl phosphate, and the unsaturated bond of oleyl phosphate and the acryloyl group of MMA are chemically bonded to form an insulating layer derived from MMA. The formed conductive particles with insulating particles were obtained.

  In the obtained conductive particles with insulating particles, the insulating layer covers the first part covering the surface of the conductive particles where the insulating particles are not disposed, and the surface of the insulating particles. The first portion and the second portion are connected to each other. The plurality of the insulating particles were not exposed by being covered with the insulating layer. The average thickness of the first part covering the surface of the part where the insulating particles of the conductive particles are not disposed was 50 nm. Of the total number of insulating particles, 85% were in contact with the conductive particles.

(Example 6)
(1) Preparation Step of Conductive Particles Nickel core material adheres on the surface of divinylbenzene resin particles, and a nickel plating layer (conductive layer) is formed on the surface of divinylbenzene resin particles so as to cover the nickel core material. ) Are formed (average particle diameter 3.01 μm, conductive layer thickness 0.10 μm, protrusion average height 350 nm).

  Except having used the prepared electroconductive particle, it carried out similarly to Example 1, and obtained the electroconductive particle with the insulating particle in which the insulating layer was formed.

(Example 7)
Conductive particles in which a nickel core material is attached on the surface of the divinylbenzene resin particles, and a nickel plating layer (conductive layer) is formed on the surface of the divinylbenzene resin particles so as to cover the nickel core material. (Average particle diameter of 2.01 μm, conductive layer thickness of 0.08 μm, protrusion average height of 100 nm) was prepared.

  Except having used the prepared electroconductive particle, it carried out similarly to Example 1, and obtained the electroconductive particle with the insulating particle in which the insulating layer was formed.

(Comparative Example 1)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the insulating layer was not formed.

(Comparative Example 2)
10 parts by weight of the conductive particles obtained in Example 1 and 1 part by weight of the insulating particles a were stirred and mixed using a hybridizer for 1 hour to form an insulating layer on the surface of the conductive particles, thereby insulating the particles. Conductive particles with a conductive layer were obtained. 10 parts by weight of the obtained conductive particles with an insulating layer and 0.5 parts by weight of the insulating particles are stirred and mixed again with a hybridizer for 15 minutes, so that the insulating particles having the insulating particles and the insulating layer are attached. Conductive particles were produced.

(Comparative Example 3)
Conductive particles with insulating particles before the formation of the insulating layer obtained in Example 1 were prepared. Oleyl phosphoric acid was dissolved in a solution containing ethanol and pure water at a weight ratio of 1: 1 to obtain a 1% by weight solution of oleyl phosphoric acid. 50 parts by weight of the conductive particles with insulating particles before formation of the obtained insulating layer were placed in 300 mL of a 1% by weight oleyl phosphoric acid solution and stirred at 50 ° C. for 1 hour to obtain a stirring solution. The obtained stirring liquid is filtered, and the collected particles are dried at 100 ° C. for 5 hours, whereby a layered insulating layer is not formed, but a compound derived from oleyl phosphate exists on the surface of the conductive particles. Conductive particles with insulating particles were obtained.

(Comparative Example 4)
Conductive particles with insulating particles before the formation of the insulating layer obtained in Example 1 were prepared. 10 parts by weight of the prepared conductive particles and 0.5 parts by weight of the insulating particles were stirred and mixed with a hybridizer for 10 minutes to produce conductive particles with insulating particles having insulating particles and an insulating layer. .

(Comparative Example 5)
Conductive particles with insulating particles before the formation of the insulating layer obtained in Example 1 were prepared.

(4) Insulating layer forming step Tetracosyl phosphate was dissolved at 70 ° C. in a solution containing ethanol and pure water at a weight ratio of 1: 1 to obtain a 1% by weight solution of tetracosyl phosphate. 10 parts by weight of conductive particles with insulating particles before formation of the prepared insulating layer is placed in 300 mL of a 1 wt% tetracosyl phosphate solution, and stirred at 70 ° C. for 3 hours to provide insulation derived from tetracosyl phosphate Conductive particles with insulating particles formed with a layer were obtained. In Comparative Example 5, the insulating layer was not formed by polymerizing a polymerizable compound.

(Evaluation)
Fabrication of connection structure:
The obtained conductive particles with insulating particles were added to “Strectbond XN-5A” manufactured by Mitsui Chemicals Co., Ltd. so as to have a content of 10% by weight, and dispersed to obtain an anisotropic conductive paste.

  A transparent glass substrate having an Al—Ti multilayer electrode pattern with L / S of 15 μm / 15 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a gold electrode pattern having L / S of 15 μm / 15 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 3 MPa is applied to form the anisotropic conductive paste layer. Completely cured at 185 ° C. to obtain a connection structure.

(1) Evaluation of conduction reliability (between upper and lower electrodes)
The connection resistance between the upper and lower electrodes of the obtained connection structure was measured by a four-terminal method. The average value of the two connection resistances was calculated. 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]
○○○: Connection resistance is 2.0Ω or less ○○: Connection resistance is over 2.0Ω, 3.0Ω or less ○: Connection resistance is over 3.0Ω, 5.0Ω or less Δ: Connection resistance is 5.0Ω Exceeding 10Ω ×: Connection resistance exceeds 10Ω

(2) Evaluation of insulation reliability (between adjacent electrodes in the horizontal direction)
In the obtained connection structure, the presence or absence of leakage between the adjacent comb-like electrodes of 100 was evaluated by measuring the resistance with a tester. Insulation reliability was judged according to the following criteria.

[Criteria for insulation reliability]
○: Resistance exceeds 500 MΩ (determined that there is no leakage)
Δ: Resistance exceeds 100 MΩ, 500 MΩ or less ×: Resistance is 100 MΩ or less (determined that there is a leak)

(3) Evaluation of rust prevention performance The connection structure produced by the above insulation evaluation was left under the conditions of 85 ° C. and relative humidity of 85%. After 100 hours from the start of standing, the connection resistance between the electrodes was measured by the 4-terminal method in the same manner as described above. Rust prevention performance was judged according to the following criteria.

[Criteria for rust prevention performance]
○: The average value of the connection resistance (after leaving) is less than 150% compared to the average value of the connection resistance (before leaving) at the time of the above-described conduction reliability evaluation. Compared to the average value before leaving), the average value of connection resistance (after leaving) is increased by 150% or more.

(4) Preventing detachment of insulating particles before conductive connection In the anisotropic conductive paste obtained by the above (2) evaluation of insulating reliability, whether or not insulating particles are detached from the surface of the conductive particles. Was observed. The anti-detachment property of the insulating particles was determined according to the following criteria.

[Decision criteria for desorption prevention]
○: The ratio of the insulating particles detached from the surface of the conductive particles is extremely small (the number ratio of the detached insulating particles is less than 10%).
Δ: There are a few insulating particles detached from the surface of the conductive particles (number ratio of the detached insulating particles is 10% or more and less than 40%)
X: There are many insulating particles detached from the surface of the conductive particles (number ratio of detached insulating particles is 40% or more)

(5) Detachability of insulating particles during conductive connection In the connection structure obtained by the above (1) evaluation of conduction reliability, the insulating particles are not detached from the surface of the conductive particles or after being detached. It was evaluated whether or not there are insulating particles sandwiched between the electrode and the conductive particles.

[Judgment criteria for detachability of insulating particles]
○: Insulating particles sandwiched between electrodes and conductive particles do not exist ×: Insulating particles sandwiched between electrodes and conductive particles exist

  The results are shown in Table 1 below. In Comparative Example 3, since the rust prevention performance was low, the conduction reliability was likely to be lowered depending on the surrounding environment.

1, 1A, 1B, 1C ... conductive particles with insulating particles 2, 2A, 2B ... conductive particles 2Aa, 2Ba ... projections 3 ... insulating particles 4, 4A, 4B, 4C ... insulating layers 4a, 4Aa, 4Ba , 4Ca ... first part 4b, 4Ab, 4Bb ... second part 11 ... base particle 12, 12A, 12B ... conductive part (conductive layer)
12BA ... 1st electroconductive part 12BB ... 2nd electroconductive part 13 ... Core substance 51 ... Connection structure 52 ... 1st connection object member 52a ... 1st electrode 53 ... 2nd connection object member 53a ... 2nd Electrode 54 ... Connection part

Claims (11)

Conductive particles having at least a conductive portion on the surface;
A plurality of insulating particles disposed on a surface of the conductive particles;
An insulating layer covering the surface of a portion of the conductive particles where the insulating particles are not disposed,
The insulating layer is formed by polymerizing a polymerizable compound;
Conductive particles with insulating particles, wherein the conductive portion and the insulating particles are chemically bonded, and the conductive portion and the insulating layer are chemically bonded. The insulating particles and the insulating layer have portions in contact with each other;
The conductive particles with insulating particles according to claim 1, wherein the insulating particles and the insulating layer are chemically bonded to each other in the contacting portion.   A first portion that covers a surface of a portion of the conductive particles where the insulating particles are not disposed; a second portion that covers a surface of the insulating particles; The electroconductive particle with an insulating particle of Claim 1 or 2 which has these.   The conductive particles with insulating particles according to claim 3, wherein the first portion and the second portion are continuous.   The average thickness of the first portion covering the surface of the conductive particles in the insulating layer where the insulating particles are not disposed is ½ or less of the average particle diameter of the insulating particles. The electroconductive particle with an insulating particle of any one of Claims 1-4 which exists.   The conductive particles with insulating particles according to any one of claims 1 to 5, wherein 90% or more of the total number of the plurality of insulating particles is in contact with the conductive particles.   The conductive particles with insulating particles according to claim 1, wherein the plurality of insulating particles are not exposed by being covered with the insulating layer.   The conductive particles with insulating particles according to claim 1, wherein the conductive particles have a plurality of protrusions on the surface of the conductive portion.   The conductive particles with insulating particles according to claim 8, wherein an average particle diameter of the insulating particles is larger than an average height of the protrusions.   The electroconductive material containing the electroconductive particle with an insulating particle of any one of Claims 1-9, and binder resin. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
A connecting portion connecting the first connection target member and the second connection target member;
The connection portion is formed of the conductive particles with insulating particles according to any one of claims 1 to 9, or is formed of a conductive material including the conductive particles with insulating particles and a binder resin. And
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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