TW201122077A - Conductive particles with attached insulating particles, method for producing conductive particles with attached insulating particles, anisotropic conductive material, and connection structure - Google Patents

Abstract

Disclosed are conductive particles with attached insulating particles wherein detachment of the insulating particles from the surface of the conductive particles is difficult. Further disclosed is a method for producing said conductive particles with attached insulating particles. The conductive particles (1) with attached insulating particles are provided with conductive particles (2) having a conductive layer (5) on the surface (2a), and insulating particles (3) attached to the surface (2a) of the conductive particles (2). The insulating particles (3) have on the surface (3a) hydroxyl groups directly bonded to phosphorus atoms or hydroxyl groups directly bonded to silicon atoms. In the method for producing the conductive particles with attached insulating particles, the insulating particles (3) having on the surface (3a) hydroxyl groups directly bonded to phosphorus atoms or hydroxyl groups directly bonded to silicon atoms are attached to the surface (2a) of the conductive particles (2).

Description

201122077 VI. [Technical Field] The present invention relates to, for example, conductive particles with insulating particles which can be used for electrical connection between electrodes, a method for producing the same, and a conductive method using the same An anisotropic conductive material of a particle and a bonded structure. [Prior Art] Heterogeneous! ·Original conductive paste, anisotropic conductive ink, anisotropic conductive adhesive sheet J anisotropic conductive film, and anisotropic conductive material such as anisotropic conductive material are widely known. Conductive particles are scattered in the ink or resin. The anisotropic conductive material can be used, for example, to electrically connect electrodes between substrates such as a glass substrate and a printed circuit board. As an example of the above-mentioned conductive particles, in the following Patent Document, there is disclosed an insulating layer comprising at least a part of a surface having a polar group and an insulating layer covering at least a part of a surface of the conductive substance i I s s 2 of the material is conductive, particles. Among them, an anisotropic conductive adhesive composition comprising the coated conductive particles and an adhesive is also disclosed. The insulating material contains a polarity that can be adsorbed on the surface of the conductive particles. The polymer electrolyte and the inorganic particles that can be adsorbed to the polymer electrolyte are insulating particles. The above-mentioned coated conductive particles are exemplified by at least one of the 34-molecular electric enamel electrostatically-absorbing (four) conductive surfaces. . The above-mentioned inorganic acid salt particles are subjected to electrostatic adsorption = the above-mentioned polymer electrolyte 'is a polyanion having a negatively chargeable functional group such as rhein, sulfuric acid and bismuth, and a four-stage clock base I5067J .doc 201122077 and polycations such as amine groups which can be positively charged. Further, Patent Document 4 listed below discloses coated conductive particles including conductive particles and a resin layer covering the surface of the conductive particles. The resin layer is bonded via a structure derived from a Sancha thiol compound. It is bonded to conductive particles. The resin layer is a film having a thickness of about 1 〇 nm. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-120990 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-135086 (Patent Document 3) Japanese Patent Laid-Open No. 2009-170414 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The situation in which the surface is detached. In particular, in the coated conductive particles described in Patent Documents 2 to 3, when the metal layer is a metal layer other than gold, for example, when the metal layer is a Ni layer or a state layer is exposed on the outermost surface of the metal layer, the insulating layer is insulated. The particles are easily detached from the surface of the conductive particles. For example, when the coated conductive particles are dispersed in the adhesive, the insulating particles are easily detached from the surface of the conductive particles. In the coated conductive (four) sub-document described in Patent Document 4, the conductive (tetra) sub-system is covered with a resin layer instead of the insulating particles. Such a resin layer is incapable of being sufficiently removed by the connection between the electrodes as compared with the insulating particles, and remains between the conductive particles and the electrode (4). Because (iv) 150671.doc 201122077, the reliability of the turn-on is likely to be low. It is an object of the present invention to provide conductive particles with insulating particles which are not easily detached from the surface of the conductive material, and a method for producing the same, and an anisotropic conductive and bonded structure using the conductive particles with the insulating particles. Materials The specific object of the present invention is, in particular, to provide a case where the metal layer is a metal layer other than gold, for example, when the metal layer is a layer or the Ni layer is exposed at the outermost surface of the metal layer, the insulating particles are not easily self-conductive particles. Conductive particles with incident insulating particles and a method for producing the same, and an anisotropic conductive material and a structure for using the conductive particles with the insulating particles. [Technical means for solving the problem] According to a broad aspect of the present invention, an electroconductive particle with insulating particles is provided, which comprises conductive particles having a conductive layer on the surface and insulation on the surface of the conductive particles. a particle, and the insulating particle has a hydroxyl group directly bonded to the phosphorus atom or a hydroxyl group directly bonded to the germanium atom on the surface. ', & the conductive particles of the accompanying insulating particles of the present invention are seen in a specific aspect of the above-mentioned insulating particles having the following formula (1丨) on the surface # _ scary basis or direct bonding The hydroxyl group of the atom. 150671.doc 201122077 X1I HO—P-I 0 Formula (11) In the above formula (11), XI represents a hydroxyl group, an alkoxy group or an alkyl group of a carbon number. In another specific aspect of the conductive particles with insulating particles of the present invention, the group represented by the above formula (11) is a group represented by the following formula (11A). OH HO-P—I Ο ··· (11A) In another specific aspect of the conductive particles with insulating particles of the present invention, the insulating particles are used to directly bond to phosphorus atoms. a compound of a hydroxyl group or a compound having a bond (4) directly bonded to (4)

In the other specific aspects of the conductive particles with insulating particles of the present invention, the above-mentioned "fourth" sub-systems are such that the compounds of the formula (1) or the radicals of the formula Compound as a village material f 3J 150671.doc 201122077 X1 ... (1) H〇-. — *X2

In the above formula (i), xi represents a hydroxyl group, an alkoxy group or an alkyl group having a carbon number of 丨~12. X2 represents an organic group having an unsaturated bond. Further, in the other specific sample of the conductive particles with insulating particles of the present invention, the compound represented by the above formula (1) is a compound represented by the following formula (1A). [Chemical 4]

OH ...(1A) HO-p-γ〇

I Ο In the above formula (1A), X2 represents an organic group having an unsaturated bond. In another specific aspect of the conductive particles with insulating particles of the present invention, the conductive particles include a substrate particle and a conductive layer covering a surface of the substrate particle. In still another specific aspect of the conductive particles with insulating particles of the present invention, the conductive particles with insulating particles are §·5 § 23 (): dispersion dispersed in 50 g of ion-exchanged water When the liquid is obtained by removing the conductive particles with the insulating particles from the dispersion to obtain a liquid at 1 Torr (rc), the conductivity of the obtained liquid is 2 〇pS/cm or less. In other specific aspects of the conductive particles, when 0.03 g of conductive particles with insulating particles are dispersed at 23 〇c in 150671.doc 201122077 toluene io g, the heat of the dispersion is conductive particles with insulating particles. Further, in the other specific aspect of the conductive particles with insulating particles of the present invention, the outermost surface of the conductive layer is a gold layer, a nickel layer or a palladium layer. Further, according to the present invention, Provided is a method for producing conductive particles with insulating particles, wherein the conductive particles with insulating particles include conductive particles having a conductive layer on a surface thereof and a surface attached to the conductive particles: (4) The incident insulating particles of the sub-system, wherein the surface has an insulating particle directly bonded to a hydroxyl group of the phosphorus atom or directly bonded to a hydroxyl group of the deuterium atom, and is attached to the surface of the electroconductive particle. In the method for producing a particle, 'the compound having a hydroxyl group directly bonded to a phosphorus atom or a compound having a radical bonded directly to the austenite atom is used, whereby a surface having a surface directly bonded to a moth atom is obtained. Or the above-mentioned insulation which is directly bonded to (a) of 7 atoms: the anisotropic conductive material of the invention comprises the conductive particles and the binder resin which are formed according to the present invention, and the connecting structure includes the first (1) a connection target member, a second connection to the ^ member, and a connection portion connecting the first and second connection target members, and the 兮 = portion is composed of (4) the conductive particles of the material of the present invention (4) The conductive particles of the insulating particles and the adhesive conductive material are formed. [Effects of the Invention] The conductive particle of the incidental particles of the present invention, the particles are in the form

】5〇67 丨.dOC 201122077 The surface has a hydroxyl group directly bonded to a phosphorus atom or a hydroxyl group directly bonded to a ruthenium atom, and the insulating particles adhere to the surface of the conductive particle, so that the insulating particle is less likely to be detached from the surface of the conductive particle. Therefore, when the conductive particles with the insulating particles are used for the connection between the electrodes, even if a plurality of conductive particles with insulating particles are in contact, the insulating particles are present between the adjacent conductive particles, and therefore should not be connected. It is not easy to electrically connect between adjacent electrodes. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the invention. (Electroconductive particles with insulating particles) Fig. 1 is a cross-sectional view showing conductive particles with insulating particles according to an embodiment of the present invention. As shown in FIG. 1 , the conductive particles 附带 with insulating particles include conductive particles 2 and a plurality of insulating particles attached to the surface 2 a of the conductive particles 2 . The conductive particles 2 include the substrate particles 4 and are coated with the conductive particles 2 . The conductive layer 5 of the surface 4a of the substrate particles 4. The surface of the conductive particles 2 based on the substrate particles* is coated with the coated particles coated with the conductive layer 5. Therefore, the conductive particles 2 are on the surface. It has a conductive layer 5. The insulating particles 3 are formed of a material having an insulating property. Examples of the substrate particles 4 include resin particles, inorganic particles, organic inorganic particles, and metal particles. The substrate particles 4 are preferably resin particles formed of a resin. When the conductive particles with the insulating particles are used to connect the electrodes, the conductive particles 1 with the insulating material are placed between the electrodes and then pressed, whereby the conductive particles 2 are compressed. When the substrate particles 4 are resin particles, the conductive particles 2 are easily deformed during the pressure bonding, and the contact area of the conductive particles of the conductive particles can be increased. Therefore, the conduction reliability between the electrodes can be improved. Examples of the resin for forming the resin particles include a polyolefin resin, an acrylic resin, a resin, a trimeric amine resin, a stupid resin, a knee resin, an epoxy resin, and an unsaturated polyg. Resin, saturated polyester resin, polyethylene terephthalate, poly-hard, polyphenylene sulfide, poly-acid, poly-imine, poly-imine, poly-shock steel and polystone stone Wait. The resin for forming the resin particles is preferably a polymer obtained by polymerizing a polymerizable monomer having two or more kinds of ethylene residues and groups, because the substrate particles 4 can be easily used. The hardness is controlled within a suitable range. The inorganic material for forming the above inorganic particles may, for example, be a carbon dioxide black or the like. Examples of the organic-inorganic hybrid particles include organic inorganic mixed particles formed of a crosslinked alumite polymer and an acrylic resin. In the case where the substrate particles 4 are metal particles, examples of the metal for forming the metal particles include silver, copper, ruthenium, zea, gold, and chin. The metal for forming the conductive layer 5 is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, iron, tin, lead, aluminum, cobalt, ruthenium, chrome, chin, ruthenium, ruthenium, ruthenium, ore, and the like. Alloys, etc. Further, examples of the metal include tin-doped indium oxide (IT〇, indium % 〇Xlde), and solder. Among them, tin and tin-containing alloys, nickel, copper, or gold are preferred because the connection resistance between the electrodes can be further reduced. Further to suppress (four) insulation, grain? From the point of view of the detachment, the conductive layer of 15067 丨.doc 201122077 is preferably a nickel layer or a layer, and particularly preferably a recording layer. In the present invention, even when the metal layer is a metal layer other than gold, for example, when the metal layer is a Ni layer or a Ni layer is exposed on the outermost surface of the metal layer, the insulating particles are less likely to be detached from the surface of the conductive particles. The conductive layer 5 is formed of one layer. The conductive layer may also be formed of a plurality of layers. That is, the conductive layer may have a laminated structure of two or more layers. In the case where the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer or an alloy layer containing tin and silver, more preferably a gold layer. In the case where the outermost layer is such a preferred conductive layer, the connection resistance between the electrodes can be further reduced. X, when the outermost layer is a gold layer, can further improve the resistance to the surname. In addition, when the conductive particles 附带3 of the insulating particles are dispersed in the toluene Ug, the heat generation amount of the dispersion is further increased, or the incident insulating particles in the adhesive resin or the like are further increased. From the viewpoint of the dispersibility of the conductive particles, the outermost surface of the conductive layer is preferably a gold layer, a recording layer or a layer. The method of forming the conductive layer 5 on the surface 4a of the substrate particles 4 is not particularly limited. As a method of forming the Lewis and the + layer, for example, a method of using a helmet electrolysis method, a method using an electric ore, and a physical vapor bond: a metal powder or a paste containing a metal material and a binder is applied to the substrate pellet. The second surface: the method and so on. Among them, it is preferable to use the electroless plating material η... because the formation of the electroconductive layer 5 is simple. As a method of using the above-mentioned method, the vacuum shovel, the ion shovel, and the ion are exemplified. _ 150671.doc 201122077 The average particle diameter of the conductive particles 2 is preferably in the range of 〇5 μ〇ι~1〇〇. . The lower limit of the average particle diameter of the electroconductive particle 2 is ^, and the upper limit is preferably 20 (four). When the average particle diameter of the conductive particles 2 is in the above-described preferable range, the contact area of the conductive particles 2 and the electrode can be sufficiently increased, and the conductive particles 2 which are less likely to form agglomeration when the conductive layer 5 is formed. Further, the interval between the electrodes connected via the conductive particles 2 is not excessively large, and the conductive layer 5 is not easily peeled off from the surface 4a of the substrate particles 4. The "average particle diameter" of the conductive particles 2 means a number average particle diameter. The average particle (4) of the conductive particles 2 was obtained by observing an arbitrary number of 50 conductive particles by an electron microscope or an optical microscope, and calculating an average value. The thickness of the conductive layer 5 is preferably within the range of (4). A better lower limit of the thickness of the conductive layer ^ G1 (four)' is preferably a higher limit of Μ (four). When the thickness of the conductive layer 5 is within the upper range, the material is sufficiently conductive, and the conductive particles 2 are not excessively hard, so that the conductive particles 2 can be sufficiently deformed at the time of connection between the electrodes. In the case where the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer, particularly the thickness of the gold layer in the case where the outermost layer is a gold layer, is preferably in the range of =0 to 0.5 _. The thickness of the outermost conductive layer is limited to °, 1 _. If the outermost layer of the guide "is better than the above (4), then the outermost layer == can be fully improved (four), and the electrode can be sufficiently reduced = two: the outermost layer is the gold layer The thickness of the gold layer is lower, and the cost is lower. The thickness of the conductive layer 5 can be measured, for example, by observing the cross section of the conductive particles 2 using a transmission electron microscope 150671.doc 12 201122077 (Transmission Electron Microscope). Insulating particles 3 are insulating particles 3. The insulating particles 3 are smaller than the conductive particles 2. Examples of the material constituting the insulating particles 3 include an insulating resin and an insulating inorganic material. The above-mentioned resin is exemplified as the resin for forming the resin particles as the substrate particles 4. The inorganic material to be used as the inorganic material for forming the inorganic particles as the substrate particles 4 is exemplified as the insulating inorganic material. The particle 3 has a hydroxyl group directly bonded to a phosphorus atom (hereinafter also referred to as a P-OH group) on the surface 3a, or a hydroxyl group directly bonded to a halogen atom (hereinafter Called

Si-OH group). Among them, the insulating particles 3 preferably have the above P-OH group in the surface formation because the adhesion between the conductive particles 2 and the insulating particles 3 can be further improved. The conductive particles (4) with insulating particles can be obtained by attaching the surface 3& to the surface 2a of the conductive particles 2 by having the hydroxyl group directly bonded to the phosphorus atom or the insulating particle 3 directly bonded to the hydroxyl group of the germanium atom. In the conductive particles 1 with insulating particles, for example, the insulating particles 3 are adhered to the surface 2a of the conductive particles 2 by the p_〇H group or the Si-OH group. The above p_〇H group or the above (4) η group on the surface 3a of the insulating particles 3 is strongly chemically bonded to the conductive layer 5 on the surface 2a of the conductive particles 2. This bond is extremely high in bonding force compared to a bond obtained only by van der Waals or electrostatic force. Therefore, the conductive particles 2 and the insulating particles 3 can be strongly adhered to each other, and the insulating particles 3 can be prevented from being detached from the surface 2a of the conductive particles 2. For example, when the conductive particles 1 with insulating particles are added to the resin, the insulating particles 3 are not easily detached from the surface 2a of the conductive particles 2, and the conductive particles are attached to the plurality of insulating particles. At the time of contact, the insulating particles 3 are less likely to be detached from the surface 2a of the conductive particles 2 by the impact at the time of contact. Further, the surface 3a has a plurality of insulating particles 3 of the above P_OH group or the above Si_〇H group, and the p_〇H group or the above 8丨_〇11 group are not chemically bonded to each other. Therefore, the insulating particles 3 can be attached to the surface 2a of the conductive particles 2 in a single layer instead of two or more layers. Therefore, a conductive particle king with incident insulating particles having a uniform particle diameter can be obtained. Further, when the insulating particles 3 have the above-mentioned p_〇H group or the above-mentioned _〇1^ group on the surface 3a, the conductive layer 5 or the electrode is not easily sinned by the above P-〇H group or the above (1) collar group. For example, when the insulating particles have a group containing a sulfur atom on the surface, the conductive layer 5 or the electrode may be corroded due to the group containing the sulfur atom. Since the insulating particles 3 have the above P-OH group or the above Si_0H group on the surface 33, corrosion of the conductive layer 5 or the electrode can be suppressed. The rim particle 3 has a group represented by the following formula (1)) or a straight H@ atom & Namely, the insulating particles having the surface (10) on the surface are preferably those having a surface represented by the formula (11). At this time, the insulating particles 3 are less likely to be separated from the surface of the conductive particles 2. [Chemical 5] 150671.doc 201122077 X1 ... (11) Η〇·—p~

I 0 In the above formula (11), X1 represents a hydroxyl group, an alkoxy group or an alkyl group having a carbon number of 丨12. The group represented by the above formula (11) is preferably a group represented by the following formula (11A). In this case, the adhesion of the insulating particles 3 to the conductive particles 2 can be further improved. [Chemical 6]

OH HO-P--* (11A) _ 0 Further, the insulating particles having a Si-OH group on the surface preferably have a group represented by the following formula (12) on the surface. The group represented by the following formula (12) can be introduced relatively easily to the surface 3a of the insulating particles 3. In the above formula (12), z 1 and Z 2 each represent a hydroxyl group, an alkoxy group or an alkyl group having a carbon number of 150671.doc -15 to 201122077 1 to 12. 21 and 22 may be the same or different. The preferred knives of 21 and 22 are hydroxyl groups because the insulating particles 3 can be strongly adhered to the surface 2a of the conductive particles 2. As a method of introducing the above p 〇H group or _〇11 group to the surface 3a of the insulating particles 3, a compound having a radical having a direct bond to a phosphorus atom (hereinafter also referred to as a P_OH group-containing compound) can be cited. a method of surface-treating an insulating particle with a compound directly bonded to a hydroxyl group of a halogen atom (hereinafter also referred to as a compound containing a Si 〇H group); and a material constituting the insulating particle when the insulating particle is produced The method of containing the above-mentioned p_〇H group-containing compound or the above Si-fluorenyl group-containing compound. In view of the fact that the surface 3a of the insulating particles 3 efficiently guides the above-mentioned p_〇H group or the above-mentioned ?〇η group, it is preferable to form the insulating particles 3 in the material of the insulating particles 3 A method comprising the above P_〇H group-containing compound or the above Si_〇H group-containing compound. The insulating particles 3 are preferably insulating particles using the above-mentioned p_〇H group-containing compound as a material because the adhesion between the insulating particles 3 and the conductive particles 2 can be further improved. As described above, the insulating particles 3 having a surface directly bonded to a hydroxyl group of a phosphorus atom or directly bonded to a hydroxyl group of a halogen atom can be, for example, by using a compound having a hydroxyl group directly bonded to a phosphorus atom or having a direct bond to the ruthenium. Obtained as a compound of a hydroxyl group of an atom. The method of surface-treating the insulating particles by the P_〇H group-containing compound or the Si—〇H group-containing compound may include the above P—OH group-containing compound or the above-described Si—〇H. a method of chemically bonding a compound to a surface of an insulating particle; and chemically treating a surface of the insulating particle 150671.doc •16·201122077 ′′ by using the above P-OH group-containing compound or the above Si_0H group-containing compound The method is such that the insulating particles have the above P-OH group or the above Si-OH group on the surface. The compound represented by the following formula (1) is exemplified as the compound containing the p_〇H group. X1 Formula (1) HO—·ρ χ2 0 In the above formula (1), XI represents a hydroxyl group, an alkoxy group or a group having a carbon number of 12~12. X2 represents an organic group having an unsaturated bond. In the above formula (1), XI is preferably a hydroxyl group. Namely, the compound represented by the above formula (1) is preferably a compound represented by the following formula (1A). In this case, the adhesion between the conductive particles 2 and the insulating particles 3 can be further improved. [Chemistry 9]

OH

I Formula (1A) HO-P-X2 In the above formula (1A), X2 represents an organic group containing an unsaturated bond. It is preferable that X2 in the above formula (1) and formula (1A) contains a (meth) acrylonitrile group because it can be easily copolymerized with the constituent raw materials of the insulating particles 3. Specific examples of the above P-OH group-containing compound include methacrylic acid 150671.doc 17 201122077 acid-filled methoxyacetic acid, mercapto-acrylic acid-acidic fluorenyloxypropane Oxypolyoxyethylene glycol monodecyl acrylate and acid phosphonium oxy group = oxypropylene glycol monodecyl acrylate. The P-OH group-containing person may be used alone or in combination of two or more. The compound represented by the following formula is exemplified as the Si-OH group-containing compound. [化 10] 21

I HO—Si-23 (Formula (2) 22 In the above formula (2), Z1 and Z2 each represent a hydroxyl group, an alkoxy group or an alkyl group having 1 to 12 carbon atoms, and Z3 represents an organic group having an unsaturated bond. Ζι~ζ3 may be the same, or different Z1 and Z2 are preferably a warp group, because the insulating particles 3 may be strongly adhered to the surface of the conductive particles 2. Further, Z3 preferably contains a (meth) acrylonitrile group because it can be easily copolymerized with the constituent raw materials of the insulating particles. Specific examples of the Si-containing thiol group-containing compound include vinyl group ketone sulphate and 3-mercapto propyl methoxy propyl sulphate. The above Si-OH group-containing compound can be used only! Two or more kinds may be used in combination. The particle diameter of the insulating particles 3 can be appropriately selected depending on the particle diameter of the conductive particles 2 and the use of the conductive particles conjugated with the insulating particles. The average particle diameter of the insulating particles 3 is preferably in the range of 〇〇〇5 to i μηι. The lower limit of the average particle diameter of the insulating particles 3 is 0.01 pm, and the upper limit is preferably 0.5 πηη. When the average particle size of the particles 3 is insulated, the conductive particles 2 with the insulating particle particles 1 are easily brought into contact with each other when the _ sub-segment 1 is dispersed in the bonding tree. If the particle size of the insulating particles 3 is too large, the connection between the electrodes -f removes the electrode and the conductive grain heat. The insulating particles 3' of 1 must be increased in pressure, or the "average particle diameter" of the insulating particles 3 must be added at a high temperature to indicate the number average particle diameter. The average particle diameter of the insulating particles 3 is determined in the same manner as the average particle diameter of the conductive particles 2 [the average particle diameter of the insulating particles 3 is preferably the average of the conductive particles 2 (4). The average particle diameter of the insulating particles 3 is preferably (10) (10) or more of the conductive particles. When the average particle diameter of the insulating particles 3 is 1/5 or less of the average particle diameter of the conductive material 2, for example, conductive particles with insulating particles are produced, and the insulating particles 3 can be more efficiently adhered to the conductive particles. The surface 2a of the particle 2 is. Two or more kinds of insulating particles having different particle diameters can also be used. In this case, the smaller insulating particles can be present between the surface of the conductive particles 2 (4) and the larger insulating particles, so that the conductive particles can be made smaller to expose the area. Therefore, even if a plurality of conductive particles with insulating particles are in contact, the conductive particles 2 of Hao are not easily contacted, so that it is possible to suppress the path between the adjacent electrodes. The average particle diameter of the smaller insulating particles is preferably 1/2 or less of the larger average particle diameter of the insulating particles. The number of smaller insulating particles is preferably 丨/4 or less of the number of larger insulating particles. In order to appropriately expose the surface 2a of the conductive particles 2 to the coverage of the insulating particles 3 (the coverage ratio of the insulating particles 3 to the conductive particles 2) is preferably in the range of 5 to 7 % by % 15067 I. doc 19 201122077 . The coverage ratio indicates the area of the portion covered by the insulating particles 4 in the entire surface area of the conductive particles 2. When the coating ratio is within the above-described preferable range, the adjacent conductive particles 2 are more difficult to contact, and the insulating particles 3 can be sufficiently removed even when heat and pressure are not provided to the extent necessary for the connection of the electrodes. The contact area of the insulating particles 2 adhering to the surface 2a of the conductive particles 2 is preferably 20% or less of the surface area of the insulating particles 3. In this case, the deformation of the insulating particles 2 is relatively small, and adhesion to the conductivity can be made. The thickness of the coating layer of the insulating particles 3 on the surface of the particles 2 is uniform. In other words, the insulating particles 3 between the conductive particles 2 and the electrodes can be efficiently removed during the contact between the electrodes. The lower limit of the contact area of the insulating particles 2 is not particularly limited, and as long as the insulating particles 3 adhere to the surface & of the conductive particles 2, the actual f is (4) or 0 (Fig. 2A), and the other aspects of the present invention are shown in cross section. Conductive particles with incidental particles of the embodiment. The conductive particles 11 with insulating particles shown in FIG. 2 include conductive particles 12 as gold, particles, and conductive particles. Surface 1: a plurality of insulating particles 3. Since the conductive particles 12 are metal particles, they have a conductive layer on the four sides. Such a conductive particle may have a layer as a surface, and may be a metal-coated particle or a metal particle. The metal for forming the conductive particles 12 is not particularly limited. As the genus, the metal described above is used as the metal for forming the conductive layer 5 of the conductive particles 2. Further, the conductive material has the same average particle diameter 祀 and the average particle diameter of the conductive particles 2. J5067J.doc •20- 201122077 The dispersion containing the conductive particles 〇5 gM23tT with insulating particles dispersed in 50 g of ion-exchanged water was placed at 1 Torr for 1 hr, and then the additional insulation was removed from the dispersion. When the liquid is obtained by the conductive particles of the particles, the conductivity of the liquid obtained is preferably 2 〇 0 / (; ηι or less. The conductivity of the solution is preferably H pS / cm or less. The lower the conductivity, the lower In addition, the "COND METER ES-51" manufactured by Horiba Seisakusho Co., Ltd., etc. can be used as the measuring device for the above-mentioned conductivity. The method for controlling the above conductivity can be exemplified by breaking the insulating particles. a method of not using an ionic compound in the step of conducting the conductive particles; and a method of using an ionic compound strongly bonded to the conductive particles in the step of coating the conductive particles with the insulating particles, wherein the conductivity is controlled The method is preferably a method in which the ionic compound is not used in the step of coating the conductive particles by the insulating particles, because the conductivity is controlled more When the conductive particles 〇·〇3 g with the insulating particles are dispersed in 1.0 g of toluene under 231, the heat generation amount of the dispersion liquid is preferably 10 mJ or more per 1 g of the conductive particles with the insulating particles. The heat generation amount is preferably 8 】 or more. The higher the amount of heat generation is, the more the dispersion property of the conductive particles with the insulating particles in the adhesive resin or the like can be further improved. The conductive particles can further have conductive particles arranged with excellent precision between the electrodes. Therefore, the conductive particles + it can be disposed with high precision between the electrodes, and the upper and lower electrodes to be connected can be easily connected by the conductive particles. 'The phenomenon that the conductive particles of the incidental insulating particles 150671.doc -21 · 201122077 which are agglomerated and which are not connected should be connected via a plurality of conductive particles can be suppressed. Therefore, the conduction reliability between the electrodes becomes In particular, when the calorific value is at least the above lower limit, when the binder resin is an epoxy resin, the accompanying insulating particles in the epoxy resin The dispersibility of the electric particles is high. As the measuring device for the calorific value, "TAMIII" manufactured by TA Instrument & A., etc. is preferable. The average particle of the above-mentioned conductive particles in the conductive particles with insulating particles is preferable. The enthalpy is 1 to 20 μm, and the calorific value is equal to or higher than the lower limit. Further, it is preferred that the conductive particles having the insulating particles have an average particle diameter of the conductive particles of (9) μηη, and conductivity of the insulating particles. The coverage of the particles is 5 to 70%, and the calorific value is equal to or higher than the lower limit. In these cases, the calorific value of the dispersion may be further increased, or the incident insulating particles in the adhesive resin or the like may be further increased. Dispersibility of conductive particles. Further, it is preferred that the outermost surface of the conductive layer is a gold layer, a nickel layer or a palladium layer and the calorific value is 1 〇 mJ or more. In this case, the heat of the granules can be further increased, or the dispersibility of the conductive particles with the virgin particles in the adhesive resin or the like can be further increased. Examples of the method for controlling the amount of heat generation include a method of subjecting the conductive particles to a surface treatment, a method of forming a composition of the insulating particles, and a method of surface-treating the insulating particles. Among them, the method of controlling the above-described heat setting is preferably a method of making the composition of the insulating particles suitable because the control of the calorific value is easy. 150671.doc 22· 201122077 (Anisotropic conductive material): The anisotropic conductive material of the invention comprises the present conductive particles and a binder resin. When the conductive particles having the insulating particles of the present embodiment are used in the second embodiment, the insulating particles 3 and the conductive particles 3 are attached to each other, so that the incidental particles 1 are dispersed in the bonding. In the case of the resin or the like, the insulating particles 3 are less likely to be detached from the surface 2a of the conductive particles 2.邑 粒 粒 The above-mentioned adhesive resin is not particularly limited. As the above-mentioned binder resin, an insulating resin is usually used. Examples of the above-mentioned binder resin include an ethylene resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, and an elastomer. The above-mentioned binder resin may be used alone or in combination of two or more kinds of the above-mentioned vinyl resins, and examples thereof include a vinyl acetate resin, an acrylic resin, and a styrene resin. Examples of the thermoplastic resin include a polyolefin resin, an ethylene-vinyl acetate copolymer, and a polyamide resin. Examples of the curable resin include an epoxy resin, an amine sulfonium Ss tree, a polyimide resin, and an unsaturated polyester resin. Further, the curable resin may be a room temperature curing resin, a thermosetting resin, a photohardening resin or a moisture curing resin. The above curable resin may be used in combination with a curing agent. Examples of the above thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene-butadiene-styrene block. a hydride of the segment copolymer, and a hydride of the present ethylene-isopentadiene-ethylene ethylene post-copolymer. Examples of the elastomer include styrene-butadiene copolymerized rubber 15067 丨.doc -23· 201122077, and acrylonitrile-styrene block copolymerized rubber. The anisotropic conductive material may contain, for example, a filler, a sizing agent, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, and the like, in addition to the conductive particles and the binder resin with the insulating particles. Heat stabilizer 1 stabilizer, UV absorber, lubricant 'antistatic agent or flame retardant _ agent for various additives. The method of dispersing the conductive particles with insulating particles in the above-mentioned binder resin can be carried out by using a conventionally known dispersion method'. As a gentleman in which the conductive particles of the insulating particles are dispersed in the above-mentioned binder resin, the conductive resin with the insulating particles is added to the binder resin, and only the back spear j is kneaded by a planetary mixer or the like. a method of dispersing a method in which a conductive particle containing an insulating particle is uniformly dispersed in water or an organic solvent, and then added to a binder resin by a homomixer or the like, and kneaded by a planetary mixer or the like, and dispersed. After a rare resin such as an organic solvent, a conductive particle containing an insulating particle is added, and a method of kneading by a lamp star mixer or the like is dispersed. The "monthly anisotropic conductive material can be used in the form of an anisotropic conductive paste, an anisotropic conductive ink, an anisotropic conductive adhesive, an anisotropic conductive film, or an anisotropic conductive sheet. In the case where the anisotropic conductive material containing the conductive particles with insulating particles of the present invention is used in the form of a film-like adhesive such as an anisotropic conductive film or an anisotropic conductive sheet, On the film-form adhesive containing the conductive particles with the insulating particles, a film-like adhesive containing no conductive particles with insulating particles is laminated. The content of the conductive particles with the insulating particles is not particularly limited. 150671.doc -24· 201122077 kL1 规·.- occupies s, which is preferably in the volume of 异/〇 of the anisotropic conductive material, the above m * sister The content of the conductive particles of the T insulating particles is in the range of 1 to 20% by volume. (Connection structure) Fig. 3 is a cross-sectional view schematically showing a connection structure using conductive particles according to an embodiment of the present invention. The connection structure 21 shown in FIG. 3 includes: The connection target member 22, the second connection target member 23', and the connection portion 24 for electrically connecting the i-th and second connection target members& The connecting portion 24 is made of conductive particles containing insulating particles! And forming an anisotropic conductive material of the resin 25. A plurality of electrodes are provided on the upper surface 22a of the first connection member 22. A plurality of electrodes 23b are provided on the lower surface of the second connection member member 23. The electrode 22b and the electrode 23b are laminated via the conductive particles ι with insulating particles. The electrode 22b and the electrode 231 are electrically connected by the conductive particles 2. Specific examples of the first and second connection target members 22'23 include electronic components such as a semiconductor wafer, a capacitor, and a diode, and a circuit board such as a printed circuit board, a flexible printed circuit board, and a glass substrate. The manufacturing method of the connection structure 2i is not specifically limited. In the example of the manufacture of the connection structure 21, the anisotropic conductive material is disposed between the second connection target member 22 and the second connection target member 23, and the laminate is heated and the laminate is heated. , the side of the pressurization, go. The temperature at which the laminate is heated is about 12 to 22 (about TC). The pressure at which the laminate is pressurized is about 9 to 8 〇 4 to 4.9 x 1 〇 6 Pa. 150671.doc -25· 201122077 When the laminate is heated and pressurized, the insulating particles 3 existing between the conductive particles 2 and the electrodes 22b and 23b can be eliminated. For example, when the heating and pressurization are performed, the conductive particles 2 and the electrodes 22b and 23b are present. The insulating particles 3 are melted or deformed, and the surface 2& of the conductive particles 2 is partially exposed. Further, when the heating and pressurization are performed, a large force is applied, and thus some of the insulating particles 3 may also be self-conducting. The surface 2a of the particles 2 is peeled off, and the surface 2a of the conductive particles 2 is partially exposed. The exposed portion of the surface 2a of the conductive particles 2 is in contact with the electrodes 22b and 23b, whereby the electrodes 22b and 23b can be electrically connected via the conductive particles 2. Further, as shown in Fig. 3, the insulating particles 3 are melted or deformed, whereby the layer 26 derived from the insulating particles 3 is formed around the contact portion between the conductive particles 2 and the electrodes 22b and 23b. The insulating particles 3 are on the surface 3a. Having the above p_〇H* or the above Si-OH group. The above-mentioned fluorene-based group or the above-mentioned Si_0H group is not only strongly chemically bonded to the conductive layer of the surface 2a of the conductive particles 2, but also strongly chemically bonded to the electrodes 22b and 23b formed of metal. The layer 26 of the self-insulating particles 3 is strongly chemically bonded to the electrodes 22b and 23b. Therefore, when the conductive particles 附带 with insulating particles are used, the layer 26 derived from the insulating particles 3 is strongly chemically bonded to the electrodes 22b and 23b. Therefore, the bonding strength between the conductive particles 2 and the electrodes 22b and 23b can be increased. Therefore, the connection reliability between the electrodes can be improved. Further, a modification of the connection structure 21 is shown in Fig. 4, as shown in the figure. The conductive particles ΙΑ and 1B with the insulating particles disposed between the plurality of electrodes 22b and 23b are in contact with the other conductive particles 1C and 1D with the insulating particles, and the conductive particles with the insulating particles are connected by 〜. .doc -26- 201122077 In recent years, the interval between the adjacent electrodes, the interval between the electrodes 22b, and the interval between the adjacent plurality of electrodes 23b is gradually narrowed. In some cases, the electrodes 22 adjacent to each other in the lateral direction are in contact with the conductive particles 1A to 1D to which the insulating particles are attached. When the conductive particles 1 with insulating particles are used, as long as no large force is applied, Since the insulating particles 3 are not easily detached from the surface η of the conductive particles 2, even if a plurality of conductive particles 附带 with insulating particles are in contact with each other, the insulating particles 3 are present between the conductive particles 2. Therefore, it is possible to suppress a plurality of adjacent ones. Short-circuiting of the electrodes 22b and 23b, that is, even if a plurality of V-electrochemical particles 1 with insulating particles are in contact, the plurality of electrodes 22b and 23b which are not connected to each other in the lateral direction are not easily connected by the plurality of conductive particles 2. . The present invention will be specifically described below by way of examples and comparative examples. The present invention is not limited to the following embodiments. (Production of Insulating Particles A to E and I) (1) Insulating particle A is manufactured in a 〇〇〇mL separable type with four separable covers, agitating blades, three-way rotary plug, condenser tube and thermometer In the flask, 'prepared to contain 45 mmol of glycidyl methacrylate, 380 mmol of methyl methacrylate, 13 mmol of ethylene glycol dimethacrylate, and acid phosphatoxy polyoxyethylene glycol methacrylate. 0·5 mmol, and 2,2'-azobis{2-[N-(2-carboxyethyl)indenyl]propylamine}1 mmol of monomer composition. The monomer composition was weighed into distilled water so that the solid content thereof became 10% by weight, and then stirred at 2 rpm under a nitrogen atmosphere at 60 °C. The underarm was subjected to polymerization for 24 hours. Reaction junction 150671, doc • 27· 201122077 After the bundle, 'freeze-drying' was carried out to obtain the above-mentioned p_〇H-based insulating particles A derived from the acid-type phosphonoxane polyoxyethylene glycol methacrylate. (2) Preparation of Insulating Particles B The same as the insulating particles 8 except that the above-mentioned acid-type phosphonium polyoxyethylene glycol methacrylate was changed to methacrylic acid-acid phosphonium oxyethyl ester. The insulating particles B having the above-mentioned P-OH group derived from a mercapto acrylic acid-acid ethoxylate were obtained. (3) Production of Insulating Particles C The above-mentioned acid-type phosphonium-oxypolyoxyethylene glycol methacrylate was changed to an acid-phosphorus oxide polyoxypropylene glycol monomethacrylate, and in addition to the insulating particles A. Insulating particles c having the above-mentioned P-OH group derived from acid sulfonium oxide polyoxypropylene glycol monomethacrylate were obtained in the same manner. (4) The insulating particles D were prepared in a 1000 mL separable flask equipped with four separable caps, agitating blades, a three-way rotary plug, a condenser, and a thermometer, and were prepared to contain glycidol methacrylate. 45 mmol, 380 mmol of thioglycolic acid methyl acetate, 13 mmol of ethylene glycol dimethacrylate, vinyl trihydroxy sulfonium ruthenium. 5 mmol, and 2,2'-azo double {2- [N-(2-carboxyethyl)indenyl;] propane μ mmol of the monomer composition. The monomer composition was weighed in distilled water so that the solid content ratio was 1% by weight, and then stirred at 200 rpm, and polymerization was carried out at 60 ° C for 24 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to a cold east to obtain an insulating particle D having a surface derived from the above-mentioned Si-OH group of the vinyl triion. (5) Preparation of insulating particles E 150671.doc -28 201122077 In addition to changing the vinyl trihydroxy decane to 3-methacryloxypropyl trihydroxy decane, the surface having the same surface as the insulating particles D was obtained. The above-mentioned 8 Å 〇 η based insulating particles E derived from 3-methyl propylene oxypropyl triacetate. (6) The insulating particles I were prepared in a 1000 mL separable flask equipped with four separable lids, a stirring blade, a three-way rotary plug, a condenser and a thermometer, and were prepared to contain 45 mmol of glycidyl methacrylate. Monomer combination of 380 mmol of methyl methacrylate, 13 mmol of ethylene glycol dimethacrylate, and 2,2,-azobis{2-[N-(2-carboxyethyl)indolyl]propane Things. The monomer composition was weighed in distilled water so as to have a solid content of 1% by weight, stirred at 200 rpm, and polymerized under nitrogen atmosphere at 6 Torr for 24 hours. After completion of the reaction, lyophilization was carried out to prepare insulating particles I having no p_〇H group and Si-OH group on the surface. (Preparation of conductive particles A to B) (1) Conductive particles A (the outermost layer is a nickel layer) were produced from tetrahydroquinone decane tetraacrylate having an average particle diameter of 3 μm and diethylbenzene benzene. The resin particles 丨〇g formed by the copolymerization resin are subjected to alkali degreasing, acid neutralization, and sensitization in a tin dichloride solution using a sodium hydroxide water solution, and then a palladium dichloride solution is used. The activated electroless plating is pretreated, filtered, and washed to obtain resin particles having palladium adhered to the surface of the particles. # The following electroless photo steps were carried out using the resin particles. Electroless nickel plating step: 15067I.doc • 29-201122077 The above resin particles were treated with a 10% by weight solution of an ion adsorbent for 5 minutes, and then added to a palladium sulfate 00% by weight aqueous solution. Thereafter, dimethylamine borane was added for reduction treatment, and the mixture was filtered and washed to obtain resin particles adhered thereto. Then, a sodium succinate-based weight % solution in which sodium succinate was dissolved in 5 〇〇 mL of ion-exchanged water was prepared. To the solution, 10 g of palladium-attached resin particles were added and mixed to prepare a slurry. Sulfuric acid was added to the slurry to adjust the pH of the slurry to 5. 7 is a nickel plating solution prepared by containing 10% by weight of nickel sulfate, 5% by weight of sodium hypophosphite, and 4 parts by weight of sodium bismuth oxide. /. And the above nickel plating solution of sodium succinate 2% by weight. The above-mentioned dip material adjusted to pH 5 was heated to 8 (rc), and the above (4) solution was continuously added dropwise to the polymer, and the bonding reaction was carried out for 2 G minutes to confirm the bonding reaction. It was confirmed that hydrogen generation was not caused and the plating reaction was terminated. Preparing the following (four) solution containing 20% by weight of sulfuric acid, 5% by weight of bis-fylamine, and 5% by weight of sodium bismuth oxide. In the solution after the end of the recording reaction using the above-mentioned recording solution The following mineral liquid was added dropwise, and when H was mixed, a bell reaction was carried out to form a nickel layer on the surface of the resin particles to obtain conductive particles A. The thickness of the nickel layer was (Μ) The electroless palladium produced under the production of the conductive particles β (the outermost layer is a palladium layer) is subjected to the step of using the obtained conductive particles A. The electroless plating Ι ε step:

The obtained conductive particles A 10 g were added to the ion-exchanged water 500

In the case of mL 150671.doc 201122077, it was sufficiently dispersed by an ultrasonic processor to obtain a particle suspension. The suspension was stirred while being stirred at 5 Torr, and slowly added with sulfuric acid 02.02 m〇I/L, ethylenediamine 0.04 mol/L as a correcting agent, and sodium formate 0.06 as a reducing agent. The electroless plating solution of m〇i/L and the crystal modifier is pH-free, and electroless palladium plating is performed. The electroless palladium is ended when the thickness of the palladium layer becomes 〇〇3. Then, it was washed and vacuum dried, whereby the conductive particles B having a palladium layer on the surface layer of the lock layer were obtained. (Preparation of Conductive Particles Included with Insulating Particles) (Example 1) ^ The obtained insulating particles A were dispersed in steamed water under ultrasonic irradiation to obtain an 8% by weight aqueous dispersion of insulating particles. The obtained conductive particles A H) g were dispersed in the steamed water 5 (10) red, and 4 g of the water dispersion of the insulating particles a was added, and the mixture was stirred at room temperature for 6 hours. After the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the same manner as in the first embodiment, the insulating particles (Comparative Example 1) / the insulating particles 1 and the conductive particles 8 were obtained in the same manner as in Example 1, and the conductive particles with insulating particles were supplied in the same manner as in the above. The particles I do not adhere to the conductive particles A. , Λ ^ Insulation to be obtained (Comparative Example 2) 150671.doc • 31 · 201122077 In the same manner as in Example ,, the insulating particles τ and the conductive particles B were used, and an attempt was made to obtain conductive particles with insulating particles. However, the insulating particles I do not adhere to the conductive particles B. (Evaluation) (1) Coverage ratio The obtained conductive particles with insulating particles were observed using a scanning electron microscope (SEM, Scanning Ε1_〇η Microscope). The coverage of the conductive particles with the insulating particles was measured by image analysis of S E Μ. In the SEM image, a circle having a diameter of half the diameter of the conductive particles with insulating particles is drawn, and the coverage of the conductive particles with the insulating particles in the circle is determined (the conductivity of the incident insulating particles in the circle) The projected area per particle, the number of conductive particles with insulating particles, and the projected area of conductive particles with insulating particles in the circle. (2) Adhesion of insulating particles: 10 parts by weight of epoxy resin (made by Japan Epoxy Resin Co., Ltd.) 10 parts by weight of 'acrylic rubber (weight average molecular weight: about 10,000) 40 parts by weight, microcapsule type 50 parts by weight of a hardening agent (α_ a-, 司w hX3941HP), 2 parts by weight of Shi Xi Shao coupling agent (Dongli Dao Kangding, "SH6_" manufactured by Xiyang A Division), and ethyl acetate (10) The resin composition was obtained. The conductive particles with the insulating particles were added to the resin plant at a content of 3% by volume to obtain an anisotropic conductive material. In part, the conductive particles with the anisotropic conductive material insulating particles obtained by the cleaning were taken out. SEM, 15067l.doc • 32· 201122077 Whether or not the insulating particles are separated from the surface of the conductive particles in the conductive particles of the edge particles The adhesion of the insulating particles was evaluated according to the following evaluation criteria. [Evaluation criteria for adhesion of insulating particles] 〇〇: 90% or more of the total number of insulating particles is not separated from the surface of the conductive particles 〇: 6〇% or more of the total number of insulating particles, less than 9〇% The surface of the conductive particles is not separated by Δ: 3〇% or more of the total number of insulating particles, and less than 6% of the insulating particles are not separated from the surface of the conductive particles. X: The total number of insulating particles is less than 3〇%. The surface of the conductive particles is detached. (3) The dispersibility of the conductive particles with the insulating particles is observed. (2) The anisotropic conductive material (anisotropic conductive paste) obtained in the evaluation of the adhesion 绝缘 of the insulating particles is attached. Whether or not the conductive particles of the insulating particles are sedimented, and whether or not the conductive particles of the incident insulating particles are aggregated. The absorptivity of the conductive particles with insulating particles was evaluated according to the following evaluation criteria. Knife [Evaluation criteria for dispersibility of conductive particles with insulating particles] 导电·· Conductive particles with incident insulating particles that do not form cohesion. 〇: Conductivity of incidental particles with a little agglomeration in about 250,000 Particle X: Insulation test of the particles (4) with agglomerated insulating particles which are apparently agglomerated in about 250,000. 150671.doc • 33- 201122077 The resin composition obtained in the evaluation of the adhesion of the above (2) insulating particles is The thickness after drying was applied to the release film so as to be 丨〇pm, and ethyl acetate was evaporated to obtain a first adhesive film containing no conductive particles with insulating particles. Further, the anisotropic conductive material obtained by the evaluation of the adhesion of the above-mentioned (2) insulating particles was applied to the release film so that the thickness after drying became 7 μm, and the obtained anisotropic insulating particles were obtained. The second adhesive film of the conductive particles. The second adhesive film containing the conductive particles with insulating particles obtained by bonding the obtained first conductive film containing the conductive particles with the insulating particles to the obtained second bonding film at a normal temperature, thereby obtaining a thickness of the two-layer structure 丨7 An anisotropic conductive film of μηι. The resulting anisotropic conductive film was cut into a size of 4 mm x 18 mm. =, prepared to have a comb pattern on the lower surface (the number of lines is 4 ,, the length of the overlapping portion is 2 mm, the line width is 2 〇, the line spacing is 2 〇, the line height is 18 (four), the electrode formed by gold The stone ray wafer (longitudinal 3 (7) is called yellow to two _x thickness! _). Further, a glass substrate (longitudinal 2 mm x lateral 12.5 mm x thickness! mm) prepared on the upper surface with an electrode formed by ιτ〇 is prepared. The obtained lower surface of the wafer is attached to the obtained anisotropic conductive film from the second adhesive film side. The glass substrate is stacked on the glass substrate, and the above-mentioned Si Xi wafer is laminated on the side of the anisotropic conductive film. In the case of ι and condition 2, the measurement sample was obtained. The resistance value between the electrodes of the obtained two measurement samples was measured, and the number of the measurement samples on the resistance value W (10) was counted and evaluated according to the following evaluation criteria. : 20N under pressure, heating at 150t for 3〇150671.doc -34- 201122077 Condition 2: 200 N under pressure, 2〇〇t: lower heating for 1 second [Evaluation of insulation test between adjacent electrodes Benchmark] 〇〇: The resistance value is H) The ratio of the measured sample of 8 Ω or more is 8 〇% Upper 0: The ratio of the measurement sample whose resistance value is ΙΟ8 Ω or more is 6〇% or more and less than 80% x. The ratio of the measurement sample whose resistance value is ΙΟ8 Ω or more is less than 6〇% (5) between the counter electrodes Conduction test The anisotropic conductive film obtained in the above (4) insulation test between adjacent electrodes was cut into a size of 5 mm x 5 mm. Further, a glass substrate having an IT surface on one side (longitudinal 25 mm x lateral direction 35 mmx thickness: 1 mm) is prepared after attaching an anisotropic conductive film to a central portion of the glass substrate having no surface of the ITO electrode. The electrodes are aligned opposite each other, and another piece of the above glass substrate is attached. Thereafter, a measurement sample was obtained by thermocompression bonding under the following conditions 1 and 2. The resistance value of the two measurement samples obtained by the four-terminal method was measured as the number of measurement samples having a resistance value of 5 Ω or less, and evaluated according to the following evaluation criteria. Condition 1: 20 N under pressure, 15 (heating for 30 minutes under TC, condition 2: heating under 200 N, heating at 200 ° C for 30 seconds [Evaluation criteria for conduction test between electrodes] 〇: Resistance value The ratio of the measurement sample of 5 Ω or less is 80% or more. △: The ratio of the measurement sample having a resistance value of 5 Ω or less is 60% or more, less than 80% x: The ratio of the measurement sample having a resistance value of 5 Ω or less is less than 60 % (6) Adhesion test 150671.doc -35- 201122077 The measurement sample obtained under the above conditions of the above-mentioned opposite electrode conduction test (7) was prepared. The measurement sample was subjected to hunger for 6 hours and ΐ2〇Μ6 J. After immersing for 3-5 hours, the cross section of the sample was observed by sem observation, and the presence or absence of interfacial peeling between the conductive particles and the insulating particles and between the insulating particles and the viscous sap was observed. Benchmark evaluation [Evaluation criteria for the adhesion test] 导电 · Conductive particles - Inter-insulating particles or insulating particles - No interfacial peeling between the bonding resins △: Conductive particles - Insulating particles + Inter- or Insulating particles - Adhesive resin Interfacial peeling X: Conductive particles - between insulating particles or insulation There is some micro-interface peeling between the particles_adhesive resin. (7) Conductivity The conductive particles of the insulating particles with the insulating particles of the examples or the conductive particles of the comparative example were dispersed in the ion-exchanged water 5 § using a stirrer. The dispersion was placed under 100 for 1 hour, and the conductive particles or conductive particles with insulating particles were removed from the dispersed dispersion to obtain a liquid using a passing apparatus. METER ES-51 (manufactured by Horiba Seisakusho Co., Ltd.) measured the conductivity of the obtained liquid 〇 (8) The calorific value of the conductive particles of the insulating particles of the examples and the conductive particles of the comparative example of 0·03 g were at 23 (: The dispersion was dispersed in a benzene benzene, and the conductive particles or conductive materials with insulating particles were measured using a microcalorimeter "TAMIII" (manufactured by Τ·A. Instrumenw 51) at the time of the dispersion 150671.doc • 36· 201122077 The calorific value of the particles per 1 g. The results are shown in the following Table 1. 150671.doc -37- 201122077 [1<] Comparative Example 2 A 1 C0 〇1 X 1 1 1 t (00 Comparative Example 1 - 1 < 2 〇1 X 1 1 1 1 1 00 m Example 10 Si-OH group CQ 2 〇〇〇〇0 〇0 m 00 Os Example 9 IQ Si-OH group < 2 (N 0 〇〇〇0 〇〇Ον Example 8 〇Si-OH group CQ 2 (N »〇〇〇〇〇0 〇〇ο § Example 7 〇Si-OH group| < 2 〇〇〇〇〇〇〇(Ν (N Example 6 U P-OH group CQ 2 CS 1 〇〇00 〇〇〇〇0 〇〇00 462 I Example 5 U P-OH group < 2 m 1 〇〇00 〇〇〇〇〇〇〇 387 Example 4 | CQ i P-OH group 0Q 2 00 00 〇〇00 0 〇〇ON 537 Example 3 P-OH group < 2 〇〇00 〇〇〇〇0 〇0 2280 Example 2 < P-OH group CQ 2 〇〇00 〇〇〇〇 0 〇0 Tj· Example 丨| < P-OH group < 〇〇00 〇〇〇〇0 〇0 m 300 | Conductive layer on the surface of the type of surface type is a rate (%) adhesion of insulating particles Dispersion conditions of particles 1 Condition 2 Condition 1 Condition 2 Conductivity test Conductivity (pS/cm) Calorific value (mJ) Insulating particle conductive particles 150£157671.doc ·38· 201122077 [Simple diagram] Figure 1 Yes Sectional view of the conductive particles in the insulating particles included with one embodiment of the invention. Fig. 2 is a cross-sectional view showing conductive particles with insulating particles according to another embodiment of the present invention. Fig. 3 is a partially cutaway cross-sectional view showing a bonded structure in which conductive particles with insulating particles according to an embodiment of the present invention are used. Fig. 4 is a partially cutaway cross-sectional view showing a modification of the connection structure shown in Fig. 3; [Explanation of main component symbols] 1 Conductive particles with insulating particles 1A to 1D Conductive particles with insulating particles 2 Conductive particles 2a Surface 3 Insulating particles 3a Surface 4 Substrate particles 4a Surface 5 Conductive layer 11 With ▼ insulating particles Conductive particle 12 Conductive particle 12a Surface 21 Connection structure 22 First connection object member 150671.doc -39- 201122077 22a Upper surface 22b Electrode 23 Second connection object member 23 a Lower surface 23b Electrode 24 Connection portion 25 Adhesive resin 26 Layer derived from insulating particles 150671.doc -40-

Claims (1)

201122077 VII. Patent application scope: A conductive particle with insulating particles, comprising: conductive particles having a conductive layer on a surface thereof; and insulating particles attached to a surface of the conductive particles, and the insulating particles are矣 g g, surface eight has a direct bond to the hydroxyl group of the phosphorus atom or directly bonded to the hydroxyl group of the ruthenium atom. The electroconductive particle with the insulating particles of the first aspect, wherein the above-mentioned surface has a group represented by the following formula (1)) or a hydroxyl group directly bonded to the stone atom, [Chemical I] X1 D. HO- — Ο 上 alkyl 3. As shown in the formula (11), XI represents a hydroxyl group, an alkoxy group or a conductive particle with a carbon number of 12, which is accompanied by an insulating particle (11)# - Dangan The base of the above formula is a group represented by the following formula (11A), [Chemical Formula 2] Formula (11A) Ο 150671.doc 201122077 4. 5. The incidental insulating particle of claim 1 is secret, isoelectric The particles are those in which a compound having a direct bond name, a ruthenium, a hydroxyl group at a phosphorus atom, or a compound having a direct bond (tetra) atom is used as a material. The conductive particles with insulating particles, wherein the insulating particles are compounds using a compound represented by the following formula (1) or a compound having a hydroxyl group directly bonded to a ruthenium atom as a material, [Chemical 3] Χ1 ΗΟ-|-Χ2 Formula (1) Ο In the above formula (1), XI represents a hydroxyl group, an alkoxy group or a carbon group having a carbon number of diarrhea, and Χ2 represents an organic group having an unsaturated bond. 6. The conductive particle with an insulating particle according to claim 5, wherein the compound represented by the above formula (1) is a compound represented by the following formula (1): [Chemical Formula 4] ΟΗ ΗΟ·—j—X2 (ία) 0 In the above formula (1A), X2 represents an organic group containing an unsaturated bond. The conductive particles with insulating particles according to claim 1, wherein the conductive particles comprise substrate particles and a conductive layer covering a surface of the substrate particles. The conductive particles with insulating particles according to Item 2, wherein the conductive particles include substrate particles and a conductive layer covering the surface of the substrate particles. 9, such as. In the case of the third aspect, the insulating particles t-conductive particles are contained, and the conductive material in the crucible includes a substrate particle and a conductive layer covering the surface of the substrate particle. 10. The conductive particles of the insulating particles according to claim 4, wherein the conductive particles are a substrate particle and a conductive layer covering a surface of the substrate particle. The conductive particles with insulating particles according to claim 5, wherein the conductive particles comprise substrate particles and a conductive layer covering a surface of the substrate particles. The conductive particles with insulating particles according to claim 6, wherein the conductive particles comprise substrate particles and a surface layer covering the substrate particles. 13. The conductive particles of the accompanying insulating particles according to any one of claims 1 to 12, wherein the conductive particles of the accompanying insulating particles are dispersed in the ion exchange water 5 〇g Liquid in the sputum. When the crucible is left for 1 Torr, and the conductive particles with the insulating particles are removed from the dispersion to obtain a liquid, the conductivity of the obtained liquid is 汕...(10) or less. 14. The conductive particles of the insulating particles attached to any one of claims 1 to 12, wherein the conductive particles 附带3 g with the insulating particles are dispersed in toluene 1.0 g. In the middle, the amount of heat generated by the dispersion is 〇mJ or more per 1 g of the conductive particles of the insulating particles. J50671.doc 201122077 Conductive particles with insulating particles, When the conductive particles of the particles are dispersed in toluene at a temperature of 0.03, the heat generation amount of the dispersion liquid is 10 mJ or more per 1 g of the conductive particles with the insulating particles. A is attached to any one of claims 1 to 12. The conductive particles of the insulating particles, wherein the outermost surface of the conductive layer is a gold layer, a recording layer or a layer. 17. The conductive particles of the insulating particles of claim 3, wherein the outermost surface of the conductive layer is a gold layer, A nickel-plated layer or a palladium layer. The conductive particle of the insulating particles according to claim 14, wherein the outermost surface of the conductive layer is a gold layer or a nickel layer palladium layer. Conductive particles The outermost surface is a gold layer, a nickel layer or a palladium layer. 20. A method for producing conductive particles with insulating particles, the conductive particles with insulating particles comprising conductive particles having a conductive layer on a surface, and adhesion to the conductive particles The insulating particles on the surface of the particles are such that the surface has a hydroxyl group directly bonded to the phosphorus atom or an insulating particle directly bonded to the hydroxyl group of the germanium atom, and is attached to the surface of the conductive particle. A method for producing conductive particles with insulating particles, wherein a compound having a hydroxyl group directly bonded to a phosphorus atom or a compound having a hydroxyl group directly bonded to a halogen atom is used, whereby a surface having the above direct bond to a phosphorus atom is obtained a hydroxy group or the above-mentioned insulating particles directly bonded to a hydroxyl group of a ruthenium atom. 22. An anisotropic conductive material comprising the conductive particles of the accompanying insulating particles according to any one of claims 1 to 19 and a binder resin. Doc 201122077 23 , a connection structure, a dragon image member, and a first connection object, a second connection pair, and a second connection object The above-mentioned connecting portion is formed by, for example, a connecting portion of the connecting portion, and conductive particles of the particles, incidental insulation of the bismuth, or an anisotropic conductive material containing the insulating particle guide and the adhesive resin.