JP6212374B2 - Conductive particles with insulating particles, method for producing conductive particles with insulating particles, conductive material, and connection structure - Google Patents

Description

  The present invention relates to conductive particles with insulating particles in which insulating particles are attached to the surface of the conductive particles, and a method for producing conductive particles with insulating particles. Moreover, this invention relates to the electrically-conductive material and connection structure using the said electroconductive particle with an insulating particle.

  Pasty or film-like anisotropic conductive materials are widely known. In the anisotropic conductive material, a plurality of conductive particles are dispersed in a binder resin or the like.

  In order to obtain various connection structures, the anisotropic conductive material is, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)) or a connection between a semiconductor chip and a flexible printed circuit board (COF ( Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.

  Moreover, as the conductive particles, conductive particles with insulating particles in which insulating particles are arranged on the surface of the conductive particles may be used. Further, coated conductive particles in which an insulating layer is disposed on the surface of the conductive layer may be used.

  As an example of the conductive particles with insulating particles, in Patent Document 1 below, conductive particles having a polar group on at least a part of the surface and insulation covering at least a part of the surface of the conductive particles. Conductive particles with insulating particles comprising a conductive material are disclosed. Here, an anisotropic conductive adhesive composition containing the conductive particles with insulating particles and an adhesive is also disclosed. The insulating material includes a polar group on the surface of conductive particles, a polymer electrolyte that can be adsorbed, and inorganic particles that can be adsorbed to the polymer electrolyte. These inorganic particles are insulating particles. The conductive particles with insulating particles, for example, electrostatically adsorb the polymer electrolyte on at least a part of the surface of the conductive particles, and then further electrostatically adsorb the inorganic oxide particles. Can be obtained.

  As an example of the coated conductive particles, Patent Document 2 listed below discloses coated conductive particles having conductive particles and a resin layer covering the surface of the conductive particles. This resin layer is bonded to the conductive particles through a structure derived from a triazine thiol compound. The resin layer is a film having a thickness of about 10 nm.

  In addition, as an example of the conductive particles with insulating particles, the following Patent Document 3 discloses conductive composite particles in which the surface of conductive mother particles is coated with resin particles. The above coating is performed by a mixing treatment of conductive mother particles having a functional group A on the surface and resin particles having a functional group B capable of reacting with the functional group A on the surface. Patent Document 3 shows a specific example using 2,4,6-trimecapto-S-triazine in order to introduce the functional group A onto the surface of the conductive mother particles. Patent Document 3 discloses a specific example in which copper particles are used as conductive mother particles, and a specific example in which electroless nickel plating is further applied to resin particles after electroless nickel plating. In a specific example using copper particles, the conductive portion on the surface of the conductive mother particles is a conductive portion formed of copper, not a conductive portion containing nickel. In a specific example in which electroless nickel plating is further applied to the resin particles and then electroless gold plating is further performed, the conductive portion on the surface of the conductive mother particles is a conductive portion formed of gold, and in the conductive portion including nickel, Absent.

JP 2009-170414 A JP 2010-153265 A JP 2003-026813 A

  In the conductive particles with insulating particles as described in Patent Document 1, the insulating particles may be detached from the surface of the conductive particles. In particular, in the conductive particles with insulating particles described in Patent Document 1, when the conductive layer is a conductive layer other than gold, for example, the conductive layer is a Ni layer or a Ni layer on the outermost surface of the conductive layer. When is exposed, the insulating particles are easily detached from the surface of the conductive particles. For example, when the conductive particles with insulating particles are dispersed in the binder resin, the insulating particles are easily detached from the surface of the conductive particles.

  In the coated conductive particles described in Patent Document 2, the conductive particles are coated with a resin layer (insulating layer) instead of insulating particles. Such a resin layer may not be sufficiently removed by pressure bonding at the time of connection between the electrodes as compared with the insulating particles, and may remain between the conductive particles and the electrodes. For this reason, the conduction | electrical_connection reliability between electrodes tends to become low.

  In recent years, as electronic devices have become smaller and higher in performance, the L / S of the electrode width and interelectrode width has become even narrower. There is a problem that insulation failure is particularly likely to occur when such electrodes having a narrow L / S are conductively connected.

  An object of the present invention is to provide conductive particles with insulating particles and a method for producing conductive particles with insulating particles, which can improve conduction reliability and insulation reliability when used for electrical connection between electrodes, The present invention also provides a conductive material and a connection structure using the conductive particles with insulating particles.

  According to a wide aspect of the present invention, there is provided conductive particles with insulating particles comprising conductive particles having at least a conductive portion on a surface thereof and a plurality of insulating particles attached to the surface of the conductive particles. The conductive part on the surface of the conductive particles is a conductive part containing nickel, is surface-treated with a compound having a structural unit represented by the following formula (11), and has a thiol group on the surface. Using a particle and an insulating particle having a functional group capable of reacting with a thiol group on the surface, the thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle are chemically bonded. And obtained by attaching the insulating particles to the surface of the conductive particles, or surface-treated with a compound having a structural unit represented by the following formula (11) and Conductive particles having a functional group on the surface; insulating particles having a functional group on the surface; a first functional group capable of reacting with a thiol group; and a functional group capable of reacting with the functional group on the surface of the insulating particle. The first and second functional group-containing compounds having two functional groups are used to react the thiol groups in the conductive particles with the thiol groups in the first and second functional group-containing compounds. The second functional group capable of chemically bonding with a functional group and capable of reacting with the functional group on the surface of the insulating particle and the functional group on the surface of the insulating particle in the first and second functional group-containing compounds. Is provided with conductive particles with insulating particles obtained by attaching the insulating particles to the surface of the conductive particles.

Further, according to a wide aspect of the present invention, there is provided a conductive particle with insulating particles comprising conductive particles having at least a conductive part on a surface and a plurality of insulating particles attached to the surface of the conductive particles. It is a manufacturing method, Comprising: The said electroconductive part of the surface of the said electroconductive particle is an electroconductive part containing nickel, and it is surface-treated with the compound which has a structural unit represented by following formula (11), and has a thiol group. Using conductive particles on the surface and insulating particles having functional groups capable of reacting with thiol groups on the surface, thiol groups in the conductive particles and functional groups capable of reacting with thiol groups in the insulating particles Is bonded to the surface of the conductive particles to obtain conductive particles with insulating particles, or has a structural unit represented by the following formula (11). Conductive particles having a surface treatment with a compound having a thiol group on the surface, insulating particles having a functional group on the surface, a first functional group capable of reacting with a thiol group, and the surface of the insulating particle. Using the first and second functional group-containing compounds having the second functional group capable of reacting with the functional group, the thiol groups in the conductive particles and the thiols in the first and second functional group-containing compounds The first functional group capable of reacting with a group is chemically bonded, and the functional group on the surface of the insulating particle reacts with the functional group on the surface of the insulating particle in the first and second functional group-containing compounds. Conductive particles with insulating particles are obtained by chemically bonding to the second functional group to obtain the conductive particles with insulating particles by attaching the insulating particles to the surface of the conductive particles. Provided by the manufacturing method It is.

  The compound having the structural unit represented by the formula (11) is preferably a compound having a plurality of thiol groups. The compound having the structural unit represented by the formula (11) is preferably a compound having a triazine skeleton and a thiol group. The compound having a structural unit represented by the formula (11) is preferably a compound represented by the following formula (1).

  In the formula (1), X represents a thiol group, an anilino group, an alkylamino group, a vinyl group, a (meth) acryloyl group, a carboxyl group, a sulfo group, an amino group, an epoxy group, or an imide group.

  In a specific aspect of the present invention, the conductive particles with insulating particles are surface-treated with a compound having a structural unit represented by the formula (11) and have conductive thiol groups on the surface. By using an insulating particle having a functional group capable of reacting with a thiol group on the surface, chemically bonding the thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle, It is obtained by attaching the insulating particles to the surface of the conductive particles.

The conductive particles with insulating particles are surface-treated with a compound having the structural unit represented by the formula (11) and have functional groups capable of reacting with thiol groups, and conductive particles having thiol groups on the surface. And an insulating particle having a functional group capable of reacting with a portion other than a thiol group on the surface of the conductive particle, and capable of reacting with a thiol group in the conductive particle and a thiol group in the insulating particle. A functional group is chemically bonded, and a portion other than the thiol group on the surface of the conductive particle and a functional group capable of reacting with a portion other than the thiol group on the surface of the conductive particle in the insulating particle are chemically bonded. Thus, it is preferably obtained by attaching the insulating particles to the surface of the conductive particles.

  It is preferable that the conductive surface of the conductive particles with insulating particles is subjected to rust prevention treatment. It is preferable that the conductive surface of the conductive particles with insulating particles is subjected to a rust prevention treatment with a compound having an alkyl group having 6 to 22 carbon atoms.

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

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

  In the conductive particles with insulating particles according to the present invention, the conductive portion on the surface of the conductive particles is a conductive portion containing nickel, and the conductive particles with insulating particles according to the present invention further have the formula (11 ) And conductive particles having a thiol group on the surface and insulating particles having a functional group capable of reacting with the thiol group on the surface. It is obtained by attaching the insulating particles to the surface of the conductive particles by chemically bonding a thiol group in the conductive particles and a functional group capable of reacting with the thiol group in the insulating particles, or a formula Conductive particles having a surface treatment with a compound having the structural unit represented by (11) and having a thiol group on the surface, insulating particles having a functional group on the surface, and a reaction with the thiol group Thiol in the conductive particle using the first functional group and the first functional group-containing compound having the second functional group capable of reacting with the functional group on the surface of the insulating particle. A first functional group capable of reacting with a thiol group in the first and second functional group-containing compounds, and a functional group on the surface of the insulating particle and the first and second functional groups. Since it is obtained by attaching the insulating particles to the surface of the conductive particles by chemically bonding the functional group on the surface of the insulating particles in the group-containing compound with the second functional group capable of reacting. When the electrodes are electrically connected using the conductive particles with insulating particles according to the present invention, the conduction reliability and the insulation reliability can be improved.

In the method for producing conductive particles with insulating particles according to the present invention, the conductive portion on the surface of the conductive particles is a conductive particle with insulating particles that is a conductive portion containing nickel, and further according to the present invention. In the method for producing conductive particles with insulating particles, the conductive particles which are surface-treated with the compound having the structural unit represented by the formula (11) and have thiol groups on the surface, and functional groups capable of reacting with the thiol groups. By using an insulating particle having a group on the surface, the thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle are chemically bonded to the surface of the conductive particle. Conductive particles with insulating particles are obtained by attaching insulating particles, or surface-treated with a compound having a structural unit represented by formula (11) and thiol groups Conductive particles on the surface, insulating particles having a functional group on the surface, a first functional group capable of reacting with a thiol group, and a second functional group capable of reacting with the functional group on the surface of the insulating particle The first functional group capable of reacting with the thiol group in the conductive particles and the thiol group in the first and second functional group-containing compounds. A chemical bond between the functional group on the surface of the insulating particle and the second functional group capable of reacting with the functional group on the surface of the insulating particle in the first and second functional group-containing compounds. Thus, the conductive particles with insulating particles are obtained by attaching the insulating particles to the surface of the conductive particles, so that the electrodes are electrically connected using the conductive particles with insulating particles obtained. When connected, conduction reliability and It is possible to enhance the edge reliability.

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 conductive particles with insulating particles according to the first embodiment of the present invention. FIG. 6 is a schematic diagram for explaining a method for evaluating the coverage.

  Details of the present invention will be described below.

  The conductive particles with insulating particles according to the present invention include conductive particles having a conductive portion on at least a surface, and a plurality of insulating particles attached to the surface of the conductive particles. In the conductive particle with insulating particles according to the present invention, the conductive part on the surface of the conductive particle is a conductive part containing nickel. The conductive particles with insulating particles according to the present invention are surface-treated with a compound having a structural unit represented by the formula (11) and can react with the thiol group and the conductive particles having a thiol group on the surface. Using the insulating particles having a functional group on the surface, the thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle are chemically bonded to the surface of the conductive particle. It is obtained by adhering the insulating particles (Configuration 1). Alternatively, the conductive particles with insulating particles according to the present invention are surface-treated with a compound having a structural unit represented by the formula (11) and have a thiol group on the surface, and functional groups on the surface. 1st and 2nd functional group containing compound which has the 2nd functional group which can react with the 1st functional group which can react with the insulating particle which has, and the 1st functional group which can react with a thiol group, and the surface of the said insulating particle Are used to chemically bond the thiol group in the conductive particle and the first functional group capable of reacting with the thiol group in the first and second functional group-containing compounds, and on the surface of the insulating particle. By chemically bonding the functional group and the second functional group capable of reacting with the functional group on the surface of the insulating particle in the first and second functional group-containing compounds, the surface of the conductive particle is To attach insulating particles Ri obtained (configuration 2). The conductive particles with insulating particles according to the present invention may include the above configuration 1, may include the above configuration 2, and preferably include the above configuration 1.

In the method for producing conductive particles with insulating particles according to the present invention, insulating particles comprising conductive particles having at least a conductive portion on the surface, and a plurality of insulating particles attached to the surface of the conductive particles. The attached conductive particles are obtained. In the method for producing conductive particles with insulating particles according to the present invention, the conductive portion on the surface of the conductive particles is a conductive portion containing nickel. In the method for producing conductive particles with insulating particles according to the present invention, conductive particles which are surface-treated with a compound having a structural unit represented by formula (11) and have a thiol group on the surface, Using the insulating particles having a reactive functional group on the surface, the conductive particles are chemically bonded to the thiol groups in the conductive particles and the functional groups capable of reacting with the thiol groups in the insulating particles. By attaching the insulating particles to the surface, conductive particles with insulating particles are obtained (Configuration 1 ′). Alternatively, the conductive particles that are surface-treated with the compound having the structural unit represented by the formula (11) and have a thiol group on the surface, insulating particles that have a functional group on the surface, and can react with the thiol group. Using the first functional group and the first functional group-containing compound having the second functional group capable of reacting with the functional group on the surface of the insulating particle, the thiol group in the conductive particle, The first functional group capable of reacting with the thiol group in the first and second functional group-containing compounds is chemically bonded, and the functional group on the surface of the insulating particle and the first and second functional groups are contained. By attaching the insulating particles to the surface of the conductive particles by chemically bonding the second functional group capable of reacting with the functional groups on the surface of the insulating particles in the compound, the insulating particles are attached. Obtain conductive particles 2 '). The method for producing conductive particles with insulating particles according to the present invention may include the above-described configuration 1 ′, may include the above-described configuration 2 ′, and preferably includes the above-described configuration 1 ′.

  By employing the above-described configuration in the conductive particles with insulating particles according to the present invention and the method for producing the conductive particles with insulating particles according to the present invention, the insulating particles are less likely to be unintentionally detached from the conductive particles. In addition, it is possible to improve conduction reliability and insulation reliability between the electrodes. That is, when the electrodes are connected, the conductive particles with insulating particles are pressed between the electrodes, so that the insulating particles between the electrodes and the conductive particles are detached from the surface of the conductive particles. It is possible to improve the reliability of conduction between the two. On the other hand, since the insulating particles that are not arranged between the electrode and the conductive particles are difficult to be detached from the surface of the conductive particles, even if a plurality of conductive particles with insulating particles come into contact with each other, the adjacent conductive particles Since insulating particles exist between the conductive particles, electrical connection between the lateral electrodes that should not be connected can be suppressed.

  In the present invention, from the viewpoint of suppressing the detachment of the insulating particles, the conductive portion on the surface of the conductive particles is a conductive portion containing nickel. When the conductive part has a multilayer structure, the outermost layer of the conductive part is a conductive part containing nickel. By suppressing the detachment of the insulating particles, the insulation reliability between the electrodes is increased. In the present invention, the conductive portion on the surface of the conductive particles is formed of copper, and is different from a conductive portion that is formed of copper or gold and does not include nickel. It is a conductive part. When the conductive part on the surface of the conductive particle is a conductive part containing nickel, the conductive part on the surface of the conductive particle is a conductive part formed of copper and not containing nickel. In comparison, the insulation reliability is effectively increased. Further, the conductive part on the surface of the conductive particles is a conductive part containing nickel, so that the conductive part on the surface of the conductive particles is formed of gold and does not contain nickel. Compared to the case, the conduction reliability is effectively increased. In a conductive portion made of gold and not containing nickel, the conductive portion is relatively soft, so that foreign matters and oxide films on the surface of the electrode cannot be sufficiently removed, and the connection resistance tends to increase. In this invention, that the said electroconductive part of the surface of the said electroconductive particle is a electroconductive part containing nickel contributes greatly to expression of the effect of this invention. Moreover, conduction | electrical_connection reliability also becomes it high that the said electroconductive part of the surface of the said electroconductive particle is an electroconductive part containing nickel.

Also, in recent years, with the downsizing and higher performance of electronic devices, the electrode width, which is the line (L) where the electrode is formed, and the space between the electrodes where the electrode is not formed (S) The width is getting narrower. For example, it is necessary to electrically connect fine electrodes having L / S of 30 μm or less / 30 μm or less. In the case of electrically connecting electrodes having a small L / S, the conventional conductive material has a problem that insulation defects are particularly likely to occur because many conductive particles with insulating particles are easily arranged in the space (S). There is.

  On the other hand, by using the conductive particles with insulating particles according to the present invention, it becomes difficult to arrange the conductive particles in the space (S), and it is possible to effectively suppress the occurrence of poor insulation. In particular, the insulation reliability can be sufficiently increased even in the case of conductive connection between fine electrodes having L / S of 30 μm or less / 30 μm or less.

  In recent years, it has been required to increase the particle size of the insulating particles attached to the surface of the conductive particles in order to increase the insulation reliability when the electrodes having a small L / S are electrically connected. ing. However, when the particle diameter of the insulating particles is increased, the insulating particles are easily detached from the surface of the conductive particles.

  On the other hand, according to the present invention, even when the particle diameter of the insulating particles is large, unintentional detachment of the insulating particles can be suppressed, and sufficient conduction reliability and insulation reliability can be ensured.

  In the conductive particles with insulating particles according to the present invention, in particular, the electrode width which is the line (L) of the portion where the electrodes (first and second electrodes) are formed, and the electrodes (first and second electrodes). When the L / S indicating the inter-electrode width of the space (S) where the electrode is not formed is 30 μm or less / 30 μm or less, the insulation reliability can be effectively increased, and the L / S is When it is 20 μm or less / 20 μm or less, the insulation reliability can be further effectively improved, and when L / S is 17.5 μm or less / 17.5 μm or less, the insulation reliability is even more effective. When L / S is 15 μm or less / 15 μm or less, the insulation reliability can be particularly effectively increased. The L / S may be 50 μm or less / 50 μm or less.

  In addition, since the conductive reliability can be enhanced by the conductive particles with insulating particles according to the present invention, the width of the electrode which is the line (L) of the portion where the electrodes (first and second electrodes) are formed. The minimum value is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 17.5 μm or less, and particularly preferably 15 μm or less. The electrode width of the line (L) is preferably larger than the average particle size of the conductive particles with insulating particles, more preferably 1.1 times or more the average particle size of the conductive particles. More preferably, it is more than twice, and it is particularly preferably 3 times or more. The electrode width of the line (L) may be 50 μm or less.

  In addition, since the insulation reliability can be enhanced by the conductive particles with insulating particles according to the present invention, the interelectrode width which is a space (S) in a portion where the electrodes (first and second electrodes) are not formed. The minimum value of is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 17.5 μm or less, and particularly preferably 15 μm or less. The width between the electrodes as the space (S) is preferably larger than the average particle diameter of the conductive particles in the conductive particles with insulating particles, and more than 1.1 times the average particle diameter of the conductive particles. Is more preferably 2 times or more, and particularly preferably 3 times or more. The inter-electrode width that is the space (S) may be 50 μm or less.

  Since the use of the conductive particles with insulating particles according to the present invention effectively increases the insulation reliability, the conductive particles with insulating particles according to the present invention is used for electrical connection between the electrodes, It is preferable that the minimum value of the inter-electrode width of the space where the electrode is not formed is 30 μm or less.

  The coverage, which is the area of the portion covered with the insulating particles in the entire surface area of the conductive particles, is preferably 40% or more, more preferably 50% or more, still more preferably more than 50%, particularly preferably. 60% or more. When the coverage is equal to or higher than the lower limit, adjacent conductive particles are more difficult to contact. The coverage is preferably 95% or less, more preferably 90% or less, still more preferably 80% or less, and particularly preferably 70% or less. If the coverage is less than or equal to the above upper limit, the insulating particles can be sufficiently eliminated without applying heat and pressure more than necessary when the electrodes are connected.

  Specifically, the coverage is determined as follows.

  100 conductive particles with insulating particles were observed by observation with a scanning electron microscope (SEM), and the coverage ratio X1 (%) of the conductive particles in the conductive particles with insulating particles (attachment rate X1 (%)) (Also called). The coverage X1 is the area (projected area) of the portion covered with the insulating particles in the entire surface area of the conductive particles.

  Specifically, as shown in FIG. 6, when the conductive particles A with insulating particles are observed from one direction with a scanning electron microscope (SEM), the outer surface of the conductive part of the conductive particles A with insulating particles One insulating particle B1 is present in the circle on the (outer peripheral edge), and the insulating particle B2 present on the circumference on the outer surface (outer peripheral edge) of the conductive portion of the conductive particle A with insulating particles is 0.00. Count as 5. The said coverage is shown by the ratio of the projection area of an insulating particle with respect to the projection area of the electroconductive particle A with an insulating particle.

  That is, the coverage is expressed by the following formula (1).

  Coverage (%) = ((((number of insulating particles in circle) × 1 + (number of insulating particles on the circumference) × 0.5) × (projected area of insulating particles)) / (insulation Projected area of conductive particles with conductive particles)) × 100 (1)

  The conductive particles with insulating particles according to the present invention are preferably dispersed in a binder resin and used as a conductive material. The conductive particles with insulating particles according to the present invention are preferably used for a paste-like conductive paste. The conductive material is preferably a conductive paste.

  When electrodes are connected using conductive particles with insulating particles, short-circuiting between adjacent electrodes that should not be connected is more difficult to occur, and there is sufficient continuity between the upper and lower electrodes to be connected. From the viewpoint of securing the conductive particles, the conductive particles with insulating particles according to the present invention are preferably used for a conductive paste having a viscosity at 25 ° C. and 2.5 rpm of more than 100 Pa · s and 1000 Pa · s or less. The viscosity of the conductive paste at 25 ° C. and 2.5 rpm is preferably more than 100 Pa · s and 1000 Pa · s or less.

  From the viewpoint of further enhancing the conduction reliability and insulation reliability between the electrodes, the coefficient of variation of the particle diameter of the conductive particles with insulating particles is preferably 8% or less, more preferably 5% or less.

  The coefficient of variation (CV value) is expressed by the following equation.

CV value (%) = (ρ / Dn) × 100
ρ: Standard deviation of particle diameter of conductive particles with insulating particles Dn: Average value of particle diameter of conductive particles with insulating particles

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

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

  A conductive particle 1 with insulating particles shown in FIG. 1 includes conductive particles 2 and a plurality of insulating particles 3 attached to the surface of the conductive particles 2. The insulating particles 3 are made of an insulating material. The insulating particles 3 are not coated particles. Insulating particles 43 described later may be used instead of the insulating particles 3.

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

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

  The conductive particles 21 with insulating particles shown in FIG. 2 include conductive particles 22 and a plurality of insulating particles 3 attached to the surface of the conductive particles 22. Insulating particles 43 described later may be used instead of the insulating particles 3.

  The conductive particle 22 includes the base particle 11 and a conductive portion 31 disposed on the surface of the base particle 11. The conductive part 31 is a conductive layer. The conductive particles 22 have a plurality of core substances 32 on the surface of the substrate particles 11. The conductive portion 31 covers the base particle 11 and the core substance 32. By covering the core substance 32 with the conductive portion 31, the conductive particle 22 has a plurality of protrusions 33 on the conductive surface. The surface of the conductive portion 31 is raised by the core substance 32, and a plurality of protrusions 33 are formed.

  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 41 with insulating particles shown in FIG. 3 includes conductive particles 42 and a plurality of insulating particles 43 attached to the surface of the conductive particles 42. The insulating particles 3 may be used instead of the insulating particles 43.

  The conductive particle 42 includes the base particle 11 and a conductive portion 51 disposed on the surface of the base particle 11. The conductive part 51 is a conductive layer. The conductive particles 42 do not have a core substance like the conductive particles 22. The conductive portion 51 has a first portion and a second portion that is thicker than the first portion. The conductive particles 42 have a plurality of protrusions 52 on the conductive surface. A portion excluding the plurality of protrusions 52 is the first portion of the conductive portion 51. The plurality of protrusions 52 are the second portions where the conductive portion 51 is thick. The insulating particles 43 are coated particles.

  The insulating particles 43 have an insulating particle main body 45 and a layer 46 covering the surface of the insulating particle main body 45. The layer 46 is preferably formed of an organic compound, and is preferably formed of a polymer compound.

The layer 46 covers the entire surface of the insulating particle main body 45. Therefore, the layer 46 is disposed between the conductive particles 42 and the insulating particle main body 45. The layer 46 may be present so as to cover at least a part of the surface of the insulating particle body, and does not need to cover the entire surface of the insulating particle body. The layer 46 is preferably disposed between the conductive particles and the insulating particle body.

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

  The conductive particles 61 with insulating particles shown in FIG. 4 include conductive particles 2, a plurality of insulating particles 3 attached to the surface of the conductive particles 2, and the conductive particles 2 and the insulating particles 3. And a coating 62 covering the surface. The coating 62 is formed by subjecting the conductive surface of particles including the conductive particles 2 and the plurality of insulating particles 3 attached to the surface of the conductive particles 2 to rust prevention. Note that the insulating particles 3 may be disposed on the surface of the conductive particles 2 after the conductive surface of the conductive particles 2 has been subjected to rust prevention treatment. The conductive particles 22 and 42 may be used instead of the conductive particles 2. Insulating particles 43 may be used instead of the insulating particles 3.

  The coating 62 does not necessarily have to cover the entire surfaces of the conductive particles 2 and the insulating particles 3. The coating 62 preferably covers the entire surfaces of the conductive particles 2, the conductive portions 12, and the insulating particles 3. It is preferable that the surfaces of the conductive particles 2, the conductive portions 12, and the insulating particles 3 are not exposed by the coating 62. Since the coating 62 covers at least a part of the surface of the conductive portion 12, rust of the conductive portion 12 can be suppressed in the portion where the coating 62 is formed.

  Hereinafter, the detail of electroconductive particle, insulating particle | grains, and a rust prevention process is demonstrated.

[Conductive particles]
In the present invention, conductive particles that are surface-treated with the compound having the structural unit represented by the formula (11) and have a thiol group on the surface are used as the conductive particles before the insulating particles are attached. It is done. Conductive particles with insulating particles can be obtained by attaching the insulating particles to the surface of the conductive particles having at least a conductive portion on the surface. The conductive part in the conductive particles is preferably a conductive layer.

  Since the thiol group can be efficiently introduced on the surface of the conductive particles, the compound having the structural unit represented by the formula (11) is preferably a compound having a plurality of thiol groups. The compound having the structural unit represented by the above formula (11) more preferably has three or more thiol groups. In such a compound, some of the thiol groups are chemically bonded to the surface of the conductive particles, and the remaining thiol groups are chemically bonded to the functional groups capable of reacting with the thiol groups in the insulating particles. be able to.

  Examples of the method for surface-treating the conductive particles with the compound having the structural unit represented by the above formula (11) include an electrolytic polymerization method and an immersion method.

  Since a thiol group can be efficiently introduced on the surface of the conductive particles, the compound having a structural unit represented by the above formula (11) is preferably a compound having a triazine skeleton and a thiol group. Since the thiol group can be efficiently introduced on the surface of the conductive particles, the compound having the structural unit represented by the above formula (11) is preferably a compound represented by the following formula (1).

In the above formula (1), X represents a thiol group, an anilino group, an alkylamino group, a vinyl group, a (meth) acryloyl group, a carboxyl group, a sulfo group, an amino group, an epoxy group or an imide group. Examples of the alkylamino group include a dibutylamino group, a dioctylamino group, a dilaurylamino group, an oleylamino group, a phenylamino group, and a stearylamino group. In the above formula (1), X may be a thiol group, an anilino group or an alkylamino group. Since many groups are chemically bonded, X in the above formula (1) is preferably a thiol group. That is, the compound represented by the above formula (1) is preferably a compound represented by the following formula (1A). In the conductive particles with insulating particles, it is preferable that the insulating particles are attached to the conductive particles through X in the above formula (1).

  The compound having the structural unit represented by the formula (11) is 2,4,6-trimercapto-s-triazine (triazinethiol), 2-di-n-butylamino-4,6-dimercapto-s-. Triazine or 2-phenylamino-4,6-dimercapto-s-triazine is preferable. Only 1 type of these compounds may be used, and 2 or more types may be used together. You may use compounds other than these. The compound having the structural unit represented by the above formula (11) is particularly preferably 2,4,6-trimercapto-s-triazine (triazine thiol).

  The conductive particles have at least a conductive portion on the surface, and the conductive portion on the surface of the conductive particles may be a conductive portion containing nickel. From the viewpoint of reducing the cost and increasing the flexibility of the conductive particles to increase the conduction reliability between the electrodes, the conductive particles are formed on the surface of the base material particles and the base material particles. It is preferable to have a conductive part arranged.

  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 more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles. The base particle may be a core-shell particle including a core and a shell disposed on the surface of the core. The core may be an organic core. The shell may be an inorganic shell.

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 high.

  Various organic materials are suitably used as the resin for forming the resin particles. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polyethylene Polyalkylene terephthalates such as 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, polya Doimido, polyether ether ketone, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer, and the like. Examples of the divinylbenzene copolymer include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.

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

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

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

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

  In the case where the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal, examples of the inorganic material for forming the substrate particles include silica and carbon black. The particles formed from 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. When the base material particles are metal particles, the metal particles are preferably copper particles. However, the substrate particles are preferably not metal particles.

  If the conductive part on the surface of the conductive particles is a conductive part containing nickel, the metal for forming the conductive part is not particularly limited. Examples of the metal include gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, tungsten, and molybdenum. , Silicon and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes becomes still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable.

  The conductive part (conductive layer) may be formed of a single layer. The conductive part may be formed of a plurality of layers. That is, the conductive part may have a laminated structure of two or more layers. When the conductive part is formed of a plurality of layers, a nickel layer is formed as the outermost layer.

  In many cases, hydroxyl groups are present on the surface of the conductive portion by oxidation. Generally, a hydroxyl group exists on the surface of a conductive part containing nickel by oxidation. The hydroxyl group on the surface of the conductive particles and the compound having the structural unit represented by the formula (11) are easily chemically bonded. By utilizing the reactivity of this hydroxyl group, a thiol group can be introduced onto the surface of the conductive particles by surface treatment with a compound having a structural unit represented by the above formula (11). Further, when the insulating particles have a functional group capable of reacting with a hydroxyl group (a portion other than a thiol group) on the surface of the conductive particles, the insulating particles can be more firmly attached to the surface of the conductive particles. it can. That is, the first chemical bond between the thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle, the hydroxyl group (part other than the thiol group) on the surface of the conductive particle, and the conductivity in the insulating particle By the second chemical bond between the functional group capable of reacting with the hydroxyl group (part other than the thiol group) on the surface of the conductive particle, the insulating particle can be more firmly attached to the surface of the conductive particle.

From the viewpoint of suppressing the detachment of the insulating particles, the conductive portion on the surface of the conductive particles is a conductive portion containing nickel. When the conductive part has a multilayer structure, the outermost layer of the conductive part is a conductive part containing nickel.

  The content of nickel is preferably 50% by weight or more in 100% by weight of the conductive part containing nickel. When the conductive part is a single layer, the content of nickel is preferably 50% by weight or more in 100% by weight of the conductive part. When the conductive part has a laminated structure and has a conductive part containing nickel and a conductive part not containing nickel, the content of nickel is 50% by weight or more in 100% by weight of the conductive part containing nickel. Is preferred. When the nickel content is 50% by weight or more, the connection resistance between the electrodes becomes considerably low. In 100% by weight of the conductive part containing nickel, the nickel content is more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. The content of nickel in 100% by weight of the conductive part containing nickel may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more. The content of nickel in 100% by weight of the conductive part containing nickel is preferably 99.85% by weight or less, more preferably 99.7% by weight or less, and still more preferably less than 99.45% by weight. When the nickel content is not less than the lower limit, the connection resistance between the electrodes is further reduced. Moreover, when there are few oxide films in the surface of an electrode and an electroconductive part, there exists a tendency for the connection resistance between electrodes to become low, so that there is much content of the said nickel.

  The conductive part containing nickel preferably contains nickel and at least one of boron and phosphorus. In the conductive part containing nickel, nickel and at least one of boron and phosphorus may be alloyed. In the conductive part containing nickel, components other than nickel, boron, and phosphorus may be used.

  The total content of boron and phosphorus in 100% by weight of the conductive part containing nickel is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, It is preferably 5% by weight or less, more preferably 4% by weight or less, still more preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less. When the total content of boron and phosphorus is not less than the above lower limit, the conductive part containing nickel becomes harder, and the oxide film on the surface of the electrode and conductive particles can be more effectively removed. The connection resistance can be further reduced. When the total content of boron and phosphorus is not more than the above upper limit, the content of nickel is relatively increased, so that the connection resistance between the electrodes is reduced.

  The content of boron in 100% by weight of the conductive part containing nickel is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, preferably 5% by weight. Below, more preferably 4% by weight or less, still more preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less. When the boron content is not less than the above lower limit, the conductive part containing nickel is further hardened, and the oxide film on the surface of the electrode and the conductive particles can be more effectively removed, and the connection resistance between the electrodes is further increased. It can be made even lower. If the boron content is less than or equal to the above upper limit, the nickel content is relatively increased, so that the connection resistance between the electrodes is reduced.

  The conductive part containing nickel preferably does not contain phosphorus or contains phosphorus, and the content of phosphorus in 100% by weight of the conductive part containing nickel is preferably less than 0.5% by weight. The content of phosphorus in the conductive part 100% by weight containing nickel is more preferably 0.3% by weight or less, and still more preferably 0.1% by weight or less. It is particularly preferable that the conductive part containing nickel does not contain phosphorus.

The measuring method of each content of nickel, boron, phosphorus, etc. in the conductive part containing nickel is not particularly limited, and various known analysis methods can be used. Examples of this measuring method include absorption spectrometry or spectrum analysis. In the above-mentioned absorption analysis method, a flame absorptiometer, an electric heating furnace absorptiometer or the like can be used. Examples of the spectrum analysis method include a plasma emission analysis method and a plasma ion source mass spectrometry method.

  When measuring the contents of nickel, boron, phosphorus, etc. in the conductive part containing nickel, it is preferable to use an ICP emission spectrometer. Examples of commercially available ICP emission analyzers include ICP emission analyzers manufactured by HORIBA.

  The method for forming the conductive part on the surface of the substrate particle is not particularly limited. As a method for forming the conductive portion, for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc. Especially, since formation of 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.

  As a method for forming a conductive portion on the surface of the substrate particle, a method based on physical collision is also effective from the viewpoint of improving productivity. As a method of forming by physical collision, for example, there is a method of coating using a theta composer (manufactured by Tokuju Kogakusha Co., Ltd.).

  The average particle diameter of the conductive particles is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, preferably 100 μm or less, more preferably 20 μm or less, and further preferably 5 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. In addition, it becomes difficult to form 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 (conductive layer) 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 portion 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 hardened, and the conductive particles are sufficiently deformed when connecting the electrodes. .

  When the conductive portion (conductive layer) is formed of a plurality of layers, the thickness of the outermost conductive portion (the conductive portion containing nickel in the outermost layer) is preferably 0.001 μm or more, more preferably 0.00. It is 01 μm or more, preferably 0.5 μm or less, more preferably 0.1 μm or less. When the thickness of the conductive portion of the outermost layer is not less than the above lower limit and not more than the above upper limit, the coating with the conductive portion of the outermost layer can be made uniform, the corrosion resistance is sufficiently high, and the connection resistance between the electrodes is sufficiently high Lower.

  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 a plurality of protrusions on the conductive surface. An oxide film is often formed on the surface of the electrode connected by the conductive particles with insulating particles. Furthermore, an oxide film is often formed on the surface of the conductive part of the conductive particles. By using conductive particles having protrusions, the oxide film is effectively eliminated by the protrusions by placing the conductive particles with insulating particles between the electrodes and then pressing them. For this reason, an electrode and electroconductive particle contact still more reliably and the connection resistance between electrodes becomes low. Furthermore, the insulating particles between the conductive particles and the electrode can be 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 conductive surface of the conductive particles, a method of forming a conductive part by electroless plating after attaching a core substance to the surface of the base particle, electroless on the surface of the base particle Examples include a method of forming a conductive part by plating, then attaching a core substance, and further forming a conductive part by electroless plating, and a method of adding a core substance in the middle of forming a conductive part by electroless plating It is done. Further, the core material is not necessarily used to form the protrusions. When the conductive portion is formed by electroless plating or the like, the protrusion can also be formed by partially varying the thickness of the conductive portion.

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

  Examples of the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. Examples include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, 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.

  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.

[Insulating particles]
The insulating particles are particles having insulating properties. The insulating particles are preferably smaller than the 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. In the case where protrusions are provided on the conductive surface of the conductive particles, the insulating particles between the conductive portion and the electrode can be easily excluded. Furthermore, since the protruding portion facilitates contact with the electrode, connection reliability is improved.

In this invention, the insulating particle which has the functional group which can react with a thiol group on the surface is used as insulating particle before making it adhere to electroconductive particle. Alternatively, in the present invention, insulating particles having functional groups on the surface are used as the insulating particles before being attached to the conductive particles, and the first functional group capable of reacting with a thiol group and the insulating particles The 1st, 2nd functional group containing compound which has the 2nd functional group which can react with the said functional group of the surface is used. The first functional group and the second functional group in the first and second functional group-containing compounds may be the same functional group or different functional groups. The same functional group may react with the thiol group and may react with the functional group on the surface of the insulating particle. A part of the plurality of the same functional groups is chemically bonded to a thiol group in the conductive particle, and a part of the plurality of the same functional groups is a function of the surface of the insulating particle. It may be chemically bonded to a group. The first and second functional group-containing compounds are capable of reacting with a thiol group and are capable of reacting with the thiol group and the first functional group that is not capable of reacting with the functional group on the surface of the insulating particle. And a second functional group capable of reacting with the functional group on the surface of the insulating particle.

  Examples of the functional group capable of reacting with a thiol group include an epoxy group, a hydroxyl group, an isocyanate group, and a thiol group. Among these, from the viewpoint of effectively promoting chemical bonding between the thiol group and the functional group capable of reacting with the thiol group, and more firmly attaching the insulating particles to the surface of the conductive particles, the reaction with the above thiol groups. A possible functional group is preferably an epoxy group.

  The insulating particles are preferably surface-treated with a compound having a functional group capable of reacting with a thiol group. For example, insulating particles having an epoxy group on the surface can be obtained by surface-treating the insulating particles with a compound having an epoxy group.

  From the viewpoint of further firmly attaching the insulating particles to the surface of the conductive particles and further improving the conduction reliability and the insulation reliability between the electrodes, the conductive particles with the insulating particles are represented by the above formula (11). Using the conductive particles having a surface treatment with a compound having a structural unit represented by formula (II) and having a thiol group on the surface and insulating particles having a functional group capable of reacting with the thiol group on the surface. It is preferably obtained by attaching the insulating particles to the surface of the conductive particles by chemically bonding a thiol group in the particles and a functional group capable of reacting with the thiol group in the insulating particles. From the viewpoint of further firmly attaching the insulating particles to the surface of the conductive particles and further enhancing the conduction reliability and the insulation reliability between the electrodes, the conductive particles with insulating particles are represented by the above formula (11). It reacts with a conductive particle having a surface treated with a compound having a structural unit represented by the formula and having a thiol group on the surface, a functional group capable of reacting with the thiol group, and a portion other than the thiol group on the surface of the conductive particle Using an insulating particle having a functional group on its surface, chemically bond (first chemical bond) a thiol group in the conductive particle and a functional group capable of reacting with a thiol group in the insulating particle, And a chemical bond between the part other than the thiol group on the surface of the conductive particle and the functional group capable of reacting with the part other than the thiol group on the surface of the conductive particle in the insulating particle (second chemical bond) By causing, it is preferably obtained by depositing the insulating particles to the surface of the conductive particles.

  The insulating particles are preferably surface-treated with a compound having a functional group capable of reacting with a thiol group and a functional group capable of reacting with a portion other than the thiol group on the surface of the conductive particle.

Examples of the functional group capable of reacting with a portion other than the thiol group on the surface of the conductive particle include a group represented by the following formula (21), a hydroxyl group directly bonded to a silicon atom (Si—OH group), and a titanium atom. A directly bonded hydroxyl group (Ti-OH group) and the like can be mentioned. Among them, from the viewpoint of effectively advancing chemical bonding between the thiol group and the functional group capable of reacting with the thiol group, and further firmly attaching the insulating particles to the surface of the conductive particles, other than the above thiol groups The functional group capable of reacting with the moiety is preferably a group represented by the following formula (21) or a hydroxyl group bonded directly to a silicon atom, and is preferably a group represented by the following formula (21).

  In said formula (21), X1 represents a hydroxyl group, an alkoxy group, or a C1-C12 alkyl group.

  From the viewpoint of more firmly attaching the insulating particles to the surface of the conductive particles, the group represented by the above formula (21) is preferably a group represented by the following formula (21A).

  From the viewpoint of more firmly attaching the insulating particles to the surface of the conductive particles, the insulating particles having a hydroxyl group directly bonded to the silicon atom on the surface have a group represented by the following formula (22) on the surface. It is preferable to have.

  In said formula (22), Z1 and Z2 respectively represent a hydroxyl group, an alkoxy group, or a C1-C12 alkyl group. Z1 and Z2 may be the same or different.

  As a method for introducing a P—OH group or a Si—OH group into the surface of the insulating particle, the insulating particle is a compound having a hydroxyl group directly bonded to a phosphorus atom (hereinafter also referred to as a P—OH group-containing compound). ), Or a method of surface treatment with a compound having a hydroxyl group directly bonded to a silicon atom (hereinafter also referred to as a Si—OH group-containing compound), and a material constituting the insulating particle in the production of the insulating particle. And a method of containing the P—OH group-containing compound or the Si—OH group-containing compound. From the viewpoint of efficiently introducing P—OH groups or Si—OH groups on the surface of the insulating particles, the P-OH group-containing compound or the material constituting the insulating particles is used in the production of the insulating particles. A method of containing a Si—OH group-containing compound is preferred.

As a method for surface-treating the insulating particles with the P-OH group-containing compound or the Si-OH group-containing compound, the P-OH group-containing compound or the Si-O is applied to the surface of the insulating particles.
A method of chemically bonding the H group-containing compound, and the surface of the insulating particles are chemically treated, so that the insulating particles are formed on the surface by the P-OH group-containing compound or the Si-OH group-containing compound. And a method of modifying the group to have a Si-OH group.

  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.

  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.

  The insulating particles are preferably organic particles or inorganic particles. The organic particles are formed using an organic compound (for example, an insulating resin). The inorganic particles are formed using an inorganic compound.

  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.

In the conductive particles with insulating particles according to the present invention, the insulating particles preferably have an insulating particle body and a layer covering at least a part of the surface of the insulating particle body. Thereby, the insulating particles are more difficult to be detached from the surface of the conductive particles by kneading in the production of the conductive material. Furthermore, when a plurality of conductive particles with insulating particles come into contact, the insulating particles are difficult to be detached from the surface of the conductive particles. In order to effectively suppress unintentional detachment of the insulating particles, the material of the insulating particles or the insulating particle main body is preferably an inorganic compound, and the insulating particles or the insulating particle main body is Inorganic particles are preferred. In order to effectively suppress unintentional detachment of the insulating particles, the layer covering at least a part of the surface of the insulating particle main body is preferably formed of an organic compound. The compound is preferably a polymer compound.

  The layer covering at least a part of the surface of the insulating particle body has a functional group capable of reacting with a thiol group, or the second function in the first and second functional group-containing compounds. It preferably has a functional group capable of reacting with a group, may have a functional group capable of reacting with a thiol group, and can react with the second functional group in the first and second functional group-containing compounds. It may preferably have a functional group, and preferably has a functional group capable of reacting with a portion other than the thiol group on the surface of the conductive particles.

  The conductive particles with insulating particles have a layer formed of a polymer compound using a polymer compound or a compound that becomes a polymer compound so as to cover at least a part of the surface of the insulating particle body. It is preferably obtained through a step of forming and obtaining insulating particles and a step of obtaining the conductive particles with insulating particles by attaching the insulating particles to the surfaces of the conductive particles having at least the conductive portion on the surface. .

  From the viewpoint of further improving the detachability of the insulating particles during thermocompression bonding, the insulating particles or the insulating particle main body is preferably inorganic particles, and is preferably silica particles. Examples of the inorganic particles include shirasu particles, hydroxyapatite particles, magnesia particles, zirconium oxide particles, aluminum oxide particles, silicon carbide particles, silicon nitride particles, aluminum nitride particles, and 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 using such hard insulating particles as insulating particles are added to a binder resin and kneaded, the insulating particles are hard, so that the insulating particles are removed from the surface of the conductive particles. There is a tendency to detach easily. In the case where the insulating particles have a layer formed of the polymer compound, even if hard insulating particles are used, it is possible to suppress the separation of the hard insulating particles during the kneading.

  The layer formed of the organic compound and the layer formed of the polymer compound serve as a flexible layer, for example. The polymer compound in the layer formed of the polymer compound or the compound that becomes the polymer compound by polymerization or the like is preferably a compound having a polymerizable reactive functional group. The polymerizable reactive functional group is preferably an unsaturated double bond. For example, a compound having an unsaturated double bond (a compound that becomes a polymer compound) may be subjected to a polymerization reaction on the surface of the insulating particle main body, and the reactive functional group on the surface of the polymer compound and the insulating particle main body. And may be reacted. Examples of the polymer compound include a compound having a (meth) acryloyl group, a compound having an epoxy group, and a compound having a vinyl group. From the viewpoint of suppressing detachment of the insulating particles from the surface of the conductive particles when dispersing the conductive particles with insulating particles, the polymer compound or the compound to be the polymer compound is (meth) It preferably has at least one reactive functional group selected from the group consisting of an acryloyl group, a glycidyl group and a vinyl group. Among these, from the viewpoint of further suppressing the detachment of the insulating particles, the polymer compound or the compound to be the polymer compound preferably has a (meth) acryloyl group.

  Specific examples of the compound having the (meth) acryloyl group include methacrylic acid, hydroxyethyl acrylate, and ethylene glycol dimethacrylate.

  Specific examples of the epoxy compound include bisphenol A type epoxy resin and resorcinol glycidyl ether.

  Specific examples of the compound having a vinyl group include styrene and vinyl acetate.

  The average particle diameter of the insulating particles can be appropriately selected depending on the particle diameter of the conductive particles, the use of the conductive particles with insulating particles, and the like. The average particle diameter of the insulating particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 1 μm or less, and particularly preferably 0.5 μm or less. It is. When the average particle diameter of the insulating particles is not less than the above lower limit, the conductive particles in the plurality of conductive particles with insulating particles are difficult to contact when the conductive particles with insulating particles are dispersed in the binder resin. Become. When the average particle diameter of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating particles between the electrodes and the conductive particles when connecting the electrodes, There is no need to heat to high temperatures.

  The “average particle diameter” of the insulating particles indicates a number average particle diameter. The average particle size of the insulating particles is determined using a particle size distribution measuring device or the like.

  The average particle diameter of the insulating particles is preferably 1/2 or less of the particle diameter of the conductive particles, more preferably 1/3 or less, still more preferably 1/4 or less. / 5 or less is particularly preferable. The particle diameter of the insulating particles is preferably 1/1000 or more of the particle diameter of the conductive particles, more preferably 1/10 or more, and even more preferably more than 1/10. When the average particle diameter of the insulating particles is 1/5 or less of the particle diameter of the conductive particles, for example, when producing conductive particles with insulating particles, the insulating particles are more efficient on the surface of the conductive particles. Adheres.

  The average particle diameter of the insulating particles is preferably 0.5 times or more, more preferably 1 time or more, the thickness of the conductive part (conductive layer) in the conductive particles. The average particle diameter of the insulating particles is preferably 20 times or less, more preferably 10 times or less the thickness of the conductive part (conductive layer) in the conductive particles. When the average particle diameter of the insulating particles and the thickness of the conductive portion satisfy such a preferable relationship, the conductive particles in the plurality of conductive particles with insulating particles are difficult to contact each other, and the conductive portion and the electrode are not contacted. Insulating particles can be easily eliminated.

  The average particle diameter of the insulating particles is preferably 0.5 times or more, more preferably 1 time or more, the average particle diameter of the core substance. The average particle size of the insulating particles is preferably 20 times or less, more preferably 10 times or less, the average particle size of the core substance. When the average particle diameter of the insulating particles and the average particle diameter of the core substance satisfy such a preferable relationship, the conductive particles in the plurality of conductive particles with insulating particles are difficult to contact each other, and the conductive layer and Insulating particles between the electrodes can be easily eliminated.

  The “average particle size” of the core substance indicates a number average particle size. The average particle size of the core substance is determined using a particle size distribution measuring device or the like.

  The coefficient of variation (CV value) of the particle diameter of the insulating particles is preferably 1% or more, preferably 10% or less, more preferably 8% or less.

Two or more insulating particles having different particle diameters may be used. In this case, since small insulating particles can exist between the large insulating particles on the surface of the conductive particles, the exposed area of the conductive particles can be reduced. Therefore, even if a plurality of conductive particles with insulating particles are in contact with each other, adjacent conductive particles are difficult to contact, and thus a short circuit between adjacent electrodes can be suppressed. The average particle size of the small insulating particles is preferably 1/2 or less of the average particle size of the large insulating particles. The number of small insulating particles is preferably ¼ or less of the number of large insulating particles.

[Rust prevention treatment (film formation)]
From the viewpoint of further improving the conduction reliability, it is preferable that the conductive surface with the insulating particles has a rust preventive treatment on the conductive surface. From the viewpoint of further improving the conduction reliability, it is preferable that the conductive surface with the insulating particles has a conductive surface subjected to rust prevention with a compound having an alkyl group having 6 to 22 carbon atoms. From the viewpoint of further improving the conduction reliability, it is preferable that the conductive surface with the insulating particles has a conductive surface subjected to rust prevention with an alkyl phosphate compound or an alkyl thiol. A coating can be formed on the surface of the conductive particles with insulating particles by the rust prevention treatment. That is, conductive particles with insulating particles having a coating film are obtained.

  The coating is preferably formed of a compound having an alkyl group having 6 to 22 carbon atoms (hereinafter also referred to as compound A). The conductive particles with insulating particles are preferably surface-treated with the compound A. When the carbon number of the alkyl group is 6 or more, rust is more unlikely to occur on the surface of the conductive portion. When the carbon number of the alkyl group is 22 or less, the conductivity of the conductive particles with insulating particles is increased. 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.

  The compound A is not particularly limited as long as it has an alkyl group having 6 to 22 carbon atoms. The compound A has a phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof, a phosphite ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof, and an alkyl group having 6 to 22 carbon atoms. It is preferably at least one selected from the group consisting of alkoxysilanes, alkylthiols having an alkyl group having 6 to 22 carbon atoms, and dialkyl disulfides having an alkyl group having 6 to 22 carbon atoms. That is, the compound A having an alkyl group having 6 to 22 carbon atoms is at least one selected from the group consisting of phosphate esters or salts thereof, phosphite esters or salts thereof, alkoxysilanes, alkylthiols, and dialkyl disulfides. It is preferable that 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 even more difficult to generate, the compound A is preferably the phosphate ester or salt thereof, phosphite ester or salt thereof, or alkylthiol, and the phosphate ester or salt thereof, Or it is more preferable that it is a phosphite ester or its salt. 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 preferably has a reactive functional group capable of reacting with the conductive part. The compound A preferably has a reactive functional group capable of reacting with insulating particles. It is preferable that the coating is chemically bonded to the conductive particle portion with insulating particles (conductive particles or insulating particles) excluding the coating. The coating is preferably chemically bonded to the conductive particles, and is preferably chemically bonded to the conductive portion. The coating is preferably chemically bonded to the insulating particles. The coating is more preferably chemically bonded to the conductive particles and the insulating particles, and more preferably chemically bonded to the conductive portions and the insulating particles. Due to the presence of the reactive functional group and the chemical bond, peeling of the film is less likely to occur, and as a result, rust is less likely to occur in the conductive part, and insulating particles are not intended from the surface of the conductive particles. Makes it more difficult to detach.

Examples of the phosphoric acid ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof include, for example, phosphoric acid hexyl ester, phosphoric acid heptyl ester, phosphoric acid monooctyl ester, phosphoric acid monononyl ester, phosphoric acid monodecyl ester, Monoundecyl phosphate, monododecyl phosphate, monotridecyl phosphate, monotetradecyl phosphate, monopentadecyl phosphate, monohexyl phosphate monosodium salt, monoheptyl phosphate monosodium Salts, monooctyl phosphate monosodium salt, monononyl phosphate monosodium salt, monodecyl phosphate monosodium salt, monoundecyl phosphate monosodium salt, monododecyl phosphate monosodium salt, Phosphate mono tridecyl ester monosodium salt, phosphate acid mono tetradecyl ester monosodium salt and phosphoric acid mono pentadecyl ester monosodium salt. You may use the potassium salt of the said phosphate ester.

  Examples of the phosphite ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof include, for example, hexyl phosphite ester, heptyl phosphite ester, monooctyl phosphite ester, monononyl phosphite ester, Phosphoric acid monodecyl ester, phosphorous acid monoundecyl ester, phosphorous acid monododecyl ester, phosphorous acid monotridecyl ester, phosphorous acid monotetradecyl ester, phosphorous acid monopentadecyl ester, phosphorous acid monohexyl Ester monosodium salt, phosphorous acid monoheptyl ester monosodium salt, phosphorous acid monooctyl ester monosodium salt, phosphorous acid monononyl ester monosodium salt, phosphorous acid monodecyl ester monosodium salt, phosphorous acid monoun Decyl ester monosodium salt, phosphorous acid Dodecyl ester monosodium salt, phosphorous acid mono-tridecyl ester monosodium salt, phosphorous acid mono-tetradecyl ester monosodium salt and phosphorous acid mono-pentadecyl ester monosodium salt. You may use the potassium salt of the said phosphite.

  Examples of the alkoxysilane having an alkyl group having 6 to 22 carbon atoms include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, and nonyltri. Methoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxy Examples include silane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, and pentadecyltriethoxysilane.

  Examples of the alkyl thiol having an alkyl group having 6 to 22 carbon atoms include hexyl thiol, heptyl thiol, octyl thiol, nonyl thiol, decyl thiol, undecyl thiol, dodecyl thiol, tridecyl thiol, tetradecyl thiol, pentadecyl. Examples include thiol and hexadecyl thiol. The alkyl thiol preferably has a thiol group at the end of the alkyl chain.

  Examples of the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms include dihexyl disulfide, diheptyl disulfide, dioctyl disulfide, dinonyl disulfide, didecyl disulfide, diundecyl disulfide, didodecyl disulfide, ditridecyl disulfide, ditetradecyl disulfide. Examples include decyl disulfide, dipentadecyl disulfide, and dihexadecyl disulfide.

(Conductive material)
The conductive material according to the present invention includes the above-described conductive particles with insulating particles and a binder resin. When the conductive particles with insulating particles are used, the insulating particles are unlikely to be detached from the surface of the conductive particles when the conductive particles with insulating particles are dispersed in the binder resin. The conductive material according to the present invention is preferably an anisotropic conductive material. The conductive material according to the present invention is preferably a circuit connecting conductive material.

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

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

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

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

  The conductive material can be used as a conductive paste and a conductive film. The conductive paste may be a conductive ink or a conductive adhesive. The conductive film includes a conductive sheet. When the conductive material including the conductive particles with insulating particles is a conductive film, a film not including the conductive particles with insulating particles is laminated on the conductive film including the conductive particles with insulating particles. May be. However, as described above, the conductive material according to the present invention is preferably in a paste form, and is preferably a conductive paste. The paste form includes liquid. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

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

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

(Connection structure)
The connection structure can be obtained by connecting the connection target member using the conductive material including the conductive particles with insulating particles according to the present invention and the 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 connection target member, and the second The connection part which has connected the connection object member. The connecting portion is formed of the conductive particles with insulating particles described above, or is formed of a conductive material including the conductive particles with insulating particles and the binder resin described above. The first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles.

  FIG. 5 is a front cross-sectional view schematically showing a connection structure using conductive particles with insulating particles according to the first embodiment of the present invention.

  A connection structure 81 shown in FIG. 5 includes a first connection target member 82, a second connection target member 83, and a connection portion 84 connecting the first and second connection target members 82 and 83. Prepare. The connecting portion 84 is formed of a conductive material including the conductive particles 1 with insulating particles. The connecting portion 84 is preferably formed by curing a conductive material including a plurality of conductive particles 1 with insulating particles. In FIG. 5, the conductive particles 1 with insulating particles are schematically shown for convenience of illustration. Instead of the conductive particles 1 with insulating particles, the conductive particles with insulating particles 21, 41, 61 may be used.

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

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

  When the laminate is heated and pressed, the insulating particles 3 existing between the conductive particles 2 and the first and second electrodes 82a and 83a can be eliminated. For example, during the heating and pressurization, the insulating particles 3 existing between the conductive particles 2 and the first and second electrodes 82a and 83a are melted or deformed, The surface of the conductive particle 2 is partially exposed. Note that a large force is applied during the heating and pressurization, so that some of the insulating particles 3 are peeled off from the surface of the conductive particles 2 and the surface of the conductive particles 2 is partially exposed. Sometimes. The portion where the surface of the conductive particle 2 is exposed contacts the first and second electrodes 82a and 83a, so that the first and second electrodes 82a and 83a are electrically connected through the conductive particle 2. it can.

Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. The conductive material is preferably a conductive material for connecting electronic components. The conductive material is a paste-like conductive paste, and is preferably applied on the connection target member in a paste-like state.

  Since the insulation reliability is effectively increased by using the conductive particles with insulating particles according to the present invention, the minimum value of the inter-electrode width which is the space of the portion where the first electrode is not formed and the first It is preferable that the minimum value of the interelectrode width, which is the space of the portion where the two electrodes are not formed, is 30 μm or less.

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

  It is preferable that bumps are provided on a semiconductor chip used in a COG having a glass substrate and a semiconductor chip as connection target members.

  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 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) Conductive particle manufacturing process Conductive particles (average particle diameter of 3.01 μm, conductive layer thickness of 0.10 μm) having a nickel plating layer (conductive layer) formed on the surface of divinylbenzene resin particles are prepared. did.

  50 parts by weight of the above conductive particles and 1.5 parts by weight of 2,4,6-trimercapto-s-triazine (triazinethiol) were put in 100 mL of tetrahydrofuran (THF), and stirred at 60 ° C. for 1 hour. Obtained. The obtained stirring liquid is filtered, washed, and vacuum-dried at 120 ° C. for 5 hours. A compound derived from triazine thiol is bonded to the surface of the nickel plating layer of the conductive particles, and the thiol group is attached to the surface. Conductive particles A were obtained.

  In addition, it is TOF-SIMS ("TOF-SIMS Type-5" made by ION-TOF) that the compound derived from triazine thiol is bonded to the surface of the nickel plating layer of the conductive particles A. The functional group on the surface of the conductive particles was measured and confirmed by the presence of a functional group peak derived from triazine thiol.

(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 {2- [N- (2-carboxyethyl) amidino] propane} was added. Distilled water was added to the monomer composition so that the solid content was 10% by weight, and the mixture was stirred at 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 a (average particle diameter of 300 nm) having the above-described 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 a were dispersed in distilled water to obtain a 10 wt% dispersion of insulating particles a.

(3) Production Step of Conductive Particles with Insulating Particles Before Rust Prevention Treatment 50 parts by weight of the obtained conductive particles A 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, the thiol group in the conductive particle and the epoxy group in the insulating particle are chemically bonded, and the hydroxyl group on the surface of the nickel plating layer of the conductive particle and the P—OH group in the insulating particle are chemically bonded. In this way, insulating particles were adhered to the surface of the conductive particles to obtain conductive particles with insulating particles before rust prevention treatment.

(4) Rust prevention treatment Lauryl phosphate was dissolved in ethanol to obtain a 3% by weight solution of lauryl phosphate. The obtained conductive particles with insulating particles were put into a 3% by weight solution of lauryl phosphoric acid and stirred at 50 ° C. for 1 hour to obtain a stirring solution. The obtained stirring liquid was filtered, washed, and vacuum-dried at 50 ° C. to obtain conductive particles with insulating particles subjected to rust prevention treatment.

(Example 2)
Except that 2,4,6-trimercapto-s-triazine (triazinethiol) was changed to 2-di-n-butylamino-4,6-dimercapto-s-triazine in the process of producing conductive particles. Similarly to the conductive particle A, a conductive particle having a thiol group and an alkylamino group on the surface, to which a compound derived from 2-di-n-butylamino-4,6-dimercapto-s-triazine is bonded. B was obtained.

  Except having changed the electroconductive particle A into the electroconductive particle B, it carried out similarly to Example 1, and obtained the electroconductive particle with the insulating particle by which the antirust process was carried out. In Example 2, in addition to the chemical bond between the thiol group in the conductive particle and the epoxy group in the insulating particle, the alkylamino group in the conductive particle and the epoxy group in the insulating particle are chemically bonded. Was. That is, the insulating particles are attached to the conductive particles via the alkylamino group.

(Example 3)
Conductive particle A except that 2,4,6-trimercapto-s-triazine (triazinethiol) was changed to 2-phenylamino-4,6-dimercapto-s-triazine in the production step of conductive particles. In the same manner as above, a conductive particle C was obtained in which a compound derived from 2-phenylamino-4,6-dimercapto-s-triazine was bonded and the surface had a thiol group and an anilino group. In Example 3, in addition to the thiol group in the conductive particle and the epoxy group in the insulating particle being chemically bonded, the anilino group in the conductive particle and the epoxy group in the insulating particle were chemically bonded. It was. That is, the insulating particles were attached to the conductive particles through the anilino group.

  Except having changed the electroconductive particle A into the electroconductive particle C, it carried out similarly to Example 1, and obtained the electroconductive particle with the insulating particle by which the antirust process was carried out.

Example 4
The surface of silica particles (average particle diameter 300 nm) produced using the sol-gel method was coated with glycidyltriethoxysilane to obtain insulating particles b having epoxy groups on the surface. The obtained insulating particles b were dispersed in distilled water to obtain a 10 wt% dispersion of insulating particles b.

  Rust-proof conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the 10 wt% dispersion of insulating particles a was changed to a 10 wt% dispersion of insulating particles b. It was.

(Example 5)
In the production process of the insulating particles, the P- derived from the acid phosphooxyethyl methacrylate is the same as the insulating particles a except that the acid phosphooxypolyoxyethylene glycol methacrylate is changed to the acid phosphooxyethyl methacrylate. Insulating particles c having OH groups and epoxy groups derived from glycidyl methacrylate on the surface were obtained. The obtained insulating particles c were dispersed in distilled water to obtain a 10 wt% dispersion of insulating particles c.

  Rust-proof conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the 10 wt% dispersion of insulating particles a was changed to a 10 wt% dispersion of insulating particles c. It was.

(Example 6)
Acid phosphooxypolyoxypropylene glycol is the same as the insulating particle a except that the acid phosphooxypolyoxyethylene glycol methacrylate is changed to acid phosphooxypolyoxypropylene glycol monomethacrylate in the production process of the insulating particles. Insulating particles d having the P-OH group derived from monomethacrylate and the epoxy group derived from glycidyl methacrylate on the surface were obtained. The obtained insulating particles d were dispersed in distilled water to obtain a 10 wt% dispersion of insulating particles d.

  Rust-proof conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the 10 wt% dispersion of insulating particles a was changed to a 10 wt% dispersion of insulating particles d. It was.

(Example 7)
Insulating particles e (with P-OH groups) having the above epoxy groups derived from glycidyl methacrylate on the surface in the same manner as insulating particles a except that acid phosphooxypolyoxyethylene glycol methacrylate was not used. Not on the surface). The obtained insulating particles e were dispersed in distilled water to obtain a 10 wt% dispersion of insulating particles e.

  Rust-proof conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the 10 wt% dispersion of insulating particles a was changed to a 10 wt% dispersion of insulating particles e. It was.

(Example 8)
Conductive particles with insulating particles were obtained in the same manner as in Example 1 except that the rust prevention treatment was not performed. That is, the conductive particles with insulating particles of Example 8 are the conductive particles with insulating particles before the antirust treatment in Example 1.

Example 9
Conductive particles B obtained in Example 2 were prepared. 50 parts by weight of conductive particles B were dispersed in 300 mL of distilled water. 2 parts by weight of glycidyl methacrylate was added to the dispersion and stirred for 3 hours in a constant temperature bath at 40 ° C. to obtain conductive particles B ′ having thiol groups and methacryloyl groups on the surface.

  Moreover, the insulating particle a obtained in Example 1 was prepared. This insulating particle a was dispersed in distilled water to prepare 1 L of a 10 wt% dispersion. 2 parts by weight of 2-aminoethyl methacrylate was added to 100 parts by weight of this dispersion and stirred for 3 hours in a constant temperature bath at 40 ° C. to obtain insulating particles a ′ having a methacryloyl group on the surface. Distilled water was added to obtain a 10 wt% dispersion of insulating particles a ′ having a methacryloyl group on the surface.

  50 parts by weight of the resulting conductive particles B ′ having thiol groups and methacryloyl groups on the surface are dispersed in 300 ml of distilled water, and 2,2′-azobis {2- [N- (2-carboxyethyl) amidino] is dispersed therein. 1 part by weight of propane} was added, and 50 ml of a 10 wt% dispersion of insulating particles a ′ having a methacryloyl group on the surface was dropped while stirring at 70 ° C. and 300 rpm in a nitrogen atmosphere. By conducting polymerization at 70 ° C. for 24 hours, conductive particles with insulating particles before rust prevention treatment were obtained.

  Thereafter, in the same manner as in Example 1, conductive particles with insulating particles subjected to rust prevention treatment were obtained.

(Comparative Example 1)
Conductive particles X (average particle diameter 3.01 μm, conductive layer thickness 0.10 μm) having a nickel plating layer (conductive layer) formed on the surface of divinylbenzene resin particles were prepared.

  With the insulating particles treated with rust-proofing in the same manner as in Example 1 except that the conductive particles A were changed to the conductive particles X, that is, the conductive particles X were used without being surface-treated with triazine thiol. Conductive particles were obtained.

(Comparative Example 2)
50 parts by weight of the conductive particles A obtained in Example 1 and 3 parts by weight of glycidyl methacrylate were placed in 1 L of methanol, and subjected to ultrasonic dispersion in an ultrasonic bath at 50 ° C. for 2 hours. After dispersion, the mixture was filtered and washed with methanol to obtain conductive particles Y having an acryloyl group on the surface.

  50 parts by weight of these conductive particles Y, 3 parts by weight of 2-ethylhexyl acrylate as a polymerizable monomer, and 0.25 parts by weight of 2,2-azobis (2,4-dimethylvaleronitrile) as a thermal polymerization initiator After putting in 1 L of methanol and reacting at 50 ° C. for 10 hours, it was filtered and washed with methanol. Then, it vacuum-dried at 40 degreeC and obtained the electroconductive particle coat | covered with insulating resin (thickness 15nm).

(Comparative Example 3)
Conductive particles (average particle diameter 3.01 μm, conductive layer thickness 0.10 μm) having a nickel plating layer (conductive layer) formed on the surface of divinylbenzene resin particles were prepared.

50 parts by weight of the conductive particles and 1.5 parts by weight of octanedithiol were put in 100 mL of THF and stirred at 60 ° C. for 1 hour to obtain a stirring solution. The obtained stirring liquid was filtered, washed, and vacuum dried at 120 ° C. for 5 hours to obtain conductive particles Z. Except having changed the electroconductive particle A into the electroconductive particle Z, it carried out similarly to Example 1, and obtained the electroconductive particle with the insulating particle by which the antirust process was carried out.

(Comparative Example 4)
The conductive particles A were changed to the conductive particles X, that is, the conductive particles X were used without being surface-treated with triazine thiol, and a 10 wt% dispersion of the insulating particles a was used. Except having changed to the 10 weight% dispersion liquid, it carried out similarly to Example 1, and obtained the electroconductive particle with the insulating particle by which the antirust process was carried out.

(Comparative Example 5)
50 parts by weight of conductive particles X were dispersed in 300 mL of distilled water. 2 parts by weight of 3-methacryloxypropyltrimethoxysilane was added to the dispersion, stirred for 3 hours in a constant temperature bath at 40 ° C., filtered, and vacuum-dried at 120 ° C. for 7 hours to have a methacryloyl group on the surface. Conductive particles X ′ were obtained. The conductive particle B was changed to the conductive particle X ′, that is, the conductive particle X ′ was not surface-treated with triazine thiol to obtain a conductive particle having a methacryloyl group on the surface, and the obtained methacryloyl group was Rust-proof conductive particles with insulating particles were obtained in the same manner as in Example 9, except that the conductive particles X ′ on the surface were used.

(Comparative Example 6)
The electroconductive particle Cu which is a copper particle (average particle diameter of 3.01 micrometer) was prepared.

  The same procedure as in Example 1 was conducted except that the conductive particle A was changed to the conductive particle Cu, that is, the conductive particle Cu2 that was surface-treated with triazine thiol in the same manner as in Example 1 was used. Thus, conductive particles with insulating particles subjected to rust prevention treatment were obtained.

(Comparative Example 7)
Conductive particles Au (average particle diameter of 3.3) in which a nickel plating layer (conductive layer) is formed on the surface of the divinylbenzene resin particles and a gold layer (conductive layer) is formed on the surface of the nickel plating layer. 01 μm, nickel layer thickness 0.10 μm, gold layer thickness 0.10 μm).

  The same procedure as in Example 1 was conducted except that the conductive particle A was changed to the conductive particle Au, that is, the conductive particle Au2 which was surface-treated with triazine thiol in the same manner as in Example 1 was used. Thus, conductive particles with insulating particles subjected to rust prevention treatment were obtained.

(Evaluation)
(1) Production of anisotropic conductive paste 20 parts by weight of an epoxy compound (“EP-3300P” manufactured by Nagase ChemteX) that is a thermosetting compound and an epoxy compound (“EPICLON HP” manufactured by DIC) -4032D ") 15 parts by weight, 10 parts by weight of an amine adduct of imidazole (" PN-F "manufactured by Ajinomoto Fine Techno Co.) as a thermosetting agent, and 2-ethyl-4-methylimidazole 1 as a curing accelerator Part by weight and 20 parts by weight of alumina (average particle diameter: 0.5 μm) as a filler are blended, and the obtained conductive particles with insulating particles have a content of 10% by weight in 100% by weight of the blend. Then, an anisotropic conductive paste was obtained by stirring for 5 minutes at 2000 rpm using a planetary stirrer.

(2) Production of first connection structure (L / S = 20 μm / 20 μm) A glass substrate having an Al—Ti 4% electrode pattern (Al—Ti 4% electrode thickness 1 μm) having an L / S of 20 μm / 20 μm on the upper surface. Prepared. A semiconductor chip having a gold electrode pattern (gold electrode thickness 20 μm) with L / S of 20 μm / 20 μm on the lower surface was prepared.

  On the upper surface of the glass substrate, the anisotropic conductive paste immediately after fabrication was applied to a thickness of 20 μm to form an anisotropic conductive material layer. Next, the semiconductor chip was stacked on the upper surface of the anisotropic conductive material layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive material layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 3.0 MPa is applied to apply the anisotropic conductive material. The material layer was cured at 185 ° C. to obtain a first connection structure.

(3) Production of Second Connection Structure (L / S = 30 μm / 30 μm) A glass substrate having an Al—Ti 4% electrode pattern (Al—Ti 4% electrode thickness 1 μm) having an L / S of 30 μm / 30 μm on the upper surface Prepared. Further, a semiconductor chip having a gold electrode pattern (gold electrode thickness 20 μm) with an L / S of 30 μm / 30 μm on the lower surface was prepared.

  A second connection structure was obtained in the same manner as the production of the first connection structure except that the glass substrate and the semiconductor chip having different L / S were used.

(4) Production of Third Connection Structure (L / S = 50 μm / 50 μm) A glass substrate having an Al—Ti 4% electrode pattern (Al—Ti 4% electrode thickness 1 μm) having an L / S of 50 μm / 50 μm on the upper surface. Prepared. Further, a semiconductor chip having a gold electrode pattern (gold electrode thickness 20 μm) with an L / S of 50 μm / 50 μm on the lower surface was prepared.

  A third connection structure was obtained in the same manner as the first connection structure except that the glass substrate and the semiconductor chip having different L / S were used.

(5) Adhesiveness of insulating particles Part of the obtained conductive material (anisotropic conductive paste) was washed with toluene, and the conductive particles with insulating particles were taken out. In the extracted conductive particles with insulating particles, it was observed whether the insulating particles were detached from the surface of the conductive particles, and the adhesion of the insulating particles was evaluated according to the following evaluation criteria.

[Evaluation criteria for adhesion of insulating particles]
○○: 90% or more of the total number of insulating particles is not detached from the surface of the conductive particles ○: 60% or more and less than 90% of the total number of insulating particles are detached from the surface of the conductive particles Not separated Δ: 30% or more and less than 60% of the total number of insulating particles are not detached from the surface of the conductive particles ΔΔ: 20% or more and less than 30% of the total number of insulating particles Not desorbed from the surface of the conductive particles ×: Less than 20% of the total number of insulating particles is not desorbed from the surface of the conductive particles

(6) Viscosity The viscosity of the obtained conductive material (anisotropic conductive paste) was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 2.5 rpm rpm. The viscosity was determined according to the following criteria.

[Criteria for viscosity]
A: Over 100 Pa · s and 1000 Pa · s or less B: Not equivalent to A

(7) Disposition accuracy of conductive particles on electrode In the obtained first, second and third connection structures, conductive particles contained in a connection portion formed of a conductive material were confirmed. The ratio (%) of the number of the conductive particles arranged on the electrode and the conductive particles arranged between the electrodes was evaluated. The arrangement accuracy of the conductive particles on the electrode was determined according to the following criteria.

[Judgment criteria for placement accuracy of conductive particles on electrode]
◯: Ratio of the number of conductive particles arranged on the electrode is 70% or more ○: Ratio of the number of conductive particles arranged on the electrode is 60% or more and less than 70% Δ: On the electrode Ratio of the number of conductive particles arranged is 50% or more and less than 60% ×: Ratio of the number of conductive particles arranged on the electrode is less than 50%

(8) Conduction reliability between upper and lower electrodes In the obtained first, second, and third connection structures (n = 15), the connection resistance between the upper and lower electrodes was measured by a four-terminal method, respectively. . The average value of connection resistance 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]
○○: Average value of connection resistance is 2.0Ω or less ○: Average value of connection resistance exceeds 2.0Ω, 5.0Ω or less △: Average value of connection resistance exceeds 5.0Ω, 10.0Ω or less × : Average value of connection resistance exceeds 10.0Ω

(9) Insulation reliability between adjacent electrodes In the obtained first, second and third connection structures (n = 15), they are left in an atmosphere of 85 ° C. and 85% for 100 hours and then adjacent to each other. It was measured at 25 locations whether the electrodes were insulative or conductive. Insulation reliability was judged according to the following criteria.

[Criteria for insulation reliability]
○○: 25 places between insulated electrodes ○: 20 places or more and less than 25 places between insulated electrodes △: 15 places or more and less than 20 places between insulated electrodes △△: Insulation Between the electrodes in the state is 10 or more and less than 15 ×: Between the electrodes in the insulated state is less than 10

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Conductive particle with insulating particle 2 ... Conductive particle 3 ... Insulating particle 11 ... Base particle 12 ... Conductive part 21 ... Conductive particle with insulating particle 22 ... Conductive particle 31 ... Conductive part 32 ... Core substance 33 ... Protrusions 41 ... Conductive particles with insulating particles 42 ... Conductive particles 43 ... Insulating particles 45 ... Insulating particle main body 46 ... Layer 51 ... Conductive part 52 ... Protrusions 61 ... Conductive particles with insulating particles 62 ... Coating DESCRIPTION OF SYMBOLS 81 ... Connection structure 82 ... 1st connection object member 82a ... 1st electrode 83 ... 2nd connection object member 83a ... 2nd electrode 84 ... Connection part

Claims (20)

Conductive particles with insulating particles comprising conductive particles having at least a conductive portion on the surface, and a plurality of insulating particles attached to the surface of the conductive particles,
The conductive part on the surface of the conductive particles is a conductive part containing nickel;
Conductive particles surface-treated with a compound having a structural unit represented by the following formula (11) and having thiol groups on the surface, and insulating particles having functional groups capable of reacting with thiol groups on the surface are used. The thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle are chemically bonded to obtain the insulating particle on the surface of the conductive particle. Or
Conductive particles surface-treated with a compound having a structural unit represented by the following formula (11) and having a thiol group on the surface; insulating particles having a functional group on the surface; The first and second functional group-containing compounds having the first functional group and the second functional group capable of reacting with the functional group on the surface of the insulating particle, and the thiol group in the conductive particle and the The first functional group capable of reacting with the thiol group in the first and second functional group-containing compounds is chemically bonded, and the functional group on the surface of the insulating particle and the first and second functional group-containing compounds are combined. Insulating particles obtained by attaching the insulating particles to the surfaces of the conductive particles by chemically bonding the second functional groups capable of reacting with the functional groups on the surface of the insulating particles in With conductive particles.

  The conductive particles with insulating particles according to claim 1, wherein the compound having the structural unit represented by the formula (11) is a compound having a plurality of thiol groups.   The conductive particles with insulating particles according to claim 1 or 2, wherein the compound having the structural unit represented by the formula (11) is a compound having a triazine skeleton and a thiol group. The conductive particles with insulating particles according to any one of claims 1 to 3, wherein the compound having a structural unit represented by the formula (11) is a compound represented by the following formula (1).

In the formula (1), X represents a thiol group, an anilino group, an alkylamino group, a vinyl group, a (meth) acryloyl group, a carboxyl group, a sulfo group, an amino group, an epoxy group, or an imide group.   Conductive particles surface-treated with a compound having a structural unit represented by the formula (11) and having a thiol group on the surface, and insulating particles having a functional group capable of reacting with the thiol group on the surface are used. Then, by chemically bonding a thiol group in the conductive particle and a functional group capable of reacting with the thiol group in the insulating particle, the insulating particle is obtained by attaching the insulating particle to the surface of the conductive particle. The electroconductive particle with an insulating particle of any one of Claims 1-4. Conductive particles surface-treated with the compound having the structural unit represented by the formula (11) and having a thiol group on the surface, a functional group capable of reacting with the thiol group, and a thiol group on the surface of the conductive particle Using insulating particles having functional groups capable of reacting with other parts on the surface,
The thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle are chemically bonded, and the portion other than the thiol group on the surface of the conductive particle and the conductive particle in the insulating particle Any one of Claims 1-5 obtained by attaching the said insulating particle to the surface of the said electroconductive particle by chemically bonding the functional group which can react with parts other than the thiol group of the surface of this. Conductive particles with insulating particles according to Item. The electroconductive particle with an insulating particle of any one of Claims 1-6 by which the surface of the electroconductive part is rust-proofed. The conductive particles with insulating particles according to claim 7, wherein the surface of the conductive portion is subjected to rust prevention treatment with a compound having an alkyl group having 6 to 22 carbon atoms.   The electroconductive material containing the electroconductive particle with an insulating particle of any one of Claims 1-8, 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;
The first connection target member, and a connection portion connecting 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 8, or formed of a conductive material including the conductive particles with insulating particles and a binder resin. Has been
The connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles in the conductive particles with insulating particles. A method for producing conductive particles with insulating particles, comprising conductive particles having at least a conductive portion on the surface, and a plurality of insulating particles attached to the surface of the conductive particles,
The conductive part on the surface of the conductive particles is a conductive part containing nickel;
Conductive particles surface-treated with a compound having a structural unit represented by the following formula (11) and having thiol groups on the surface, and insulating particles having functional groups capable of reacting with thiol groups on the surface are used. Then, by chemically bonding the thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle, the insulating particle is attached to the surface of the conductive particle, thereby providing an insulating property. Obtain conductive particles with particles, or
Conductive particles surface-treated with a compound having a structural unit represented by the following formula (11) and having a thiol group on the surface; insulating particles having a functional group on the surface; The first and second functional group-containing compounds having the first functional group and the second functional group capable of reacting with the functional group on the surface of the insulating particle, and the thiol group in the conductive particle and the The first functional group capable of reacting with the thiol group in the first and second functional group-containing compounds is chemically bonded, and the functional group on the surface of the insulating particle and the first and second functional group-containing compounds are combined. By electrically bonding the second functional group capable of reacting with the functional group on the surface of the insulating particle in the above, the insulating particle is attached to the surface of the conductive particle, thereby providing conductive with insulating particle. To obtain particles, insulation Method for producing particles with conductive particles.

  The method for producing conductive particles with insulating particles according to claim 11, wherein the compound having the structural unit represented by the formula (11) is a compound having a plurality of thiol groups.   The method for producing conductive particles with insulating particles according to claim 11 or 12, wherein the compound having the structural unit represented by the formula (11) is a compound having a triazine skeleton and a thiol group. The compound having the structural unit represented by the formula (11) is a compound represented by the following formula (1), the conductive particles with insulating particles according to any one of claims 11 to 13. Production method.

In the formula (1), X represents a thiol group, an anilino group, an alkylamino group, a vinyl group, a (meth) acryloyl group, a carboxyl group, a sulfo group, an amino group, an epoxy group, or an imide group.   Conductive particles surface-treated with a compound having a structural unit represented by the formula (11) and having a thiol group on the surface, and insulating particles having a functional group capable of reacting with the thiol group on the surface are used. Then, by chemically bonding the thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle, the insulating particle is attached to the surface of the conductive particle, thereby providing an insulating property. The method for producing conductive particles with insulating particles according to claim 11, wherein conductive particles with particles are obtained. Conductive particles surface-treated with the compound having the structural unit represented by the formula (11) and having a thiol group on the surface, a functional group capable of reacting with the thiol group, and a thiol group on the surface of the conductive particle Using insulating particles having functional groups capable of reacting with other parts on the surface,
The thiol group in the conductive particle and the functional group capable of reacting with the thiol group in the insulating particle are chemically bonded, and the portion other than the thiol group on the surface of the conductive particle and the conductive particle in the insulating particle The conductive particles with insulating particles are obtained by attaching the insulating particles to the surface of the conductive particles by chemically bonding a functional group capable of reacting with a portion other than the thiol group on the surface of the conductive particles. Item 16. The method for producing conductive particles with insulating particles according to any one of Items 11 to 15. The manufacturing method of the electroconductive particle with an insulating particle of any one of Claims 11-16 which obtains the electroconductive particle with an insulating particle by carrying out the antirust process of the surface of an electroconductive part . The method for producing conductive particles with insulating particles according to claim 17, wherein the conductive particles with insulating particles are obtained by subjecting the surface of the conductive portion to rust prevention with a compound having an alkyl group having 6 to 22 carbon atoms. .   The electroconductive material containing the electroconductive particle with an insulating particle obtained by the manufacturing method of the electroconductive particle with an insulating particle of any one of Claims 11-18, 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;
The first connection target member, and a connection portion connecting the second connection target member,
The said connection part is formed with the electroconductive particle with an insulating particle obtained by the manufacturing method of the electroconductive particle with an insulating particle of any one of Claims 11-18, or with the said insulating particle. It is made of a conductive material containing conductive particles and a binder resin,
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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