TW201222558A - Conductive particles, anisotropic conductive material and connection structure - Google Patents

Abstract

Provided are: conductive particles, each of which is not susceptible to a large crack in a conductive layer even in cases where a large force is applied thereto; an anisotropic conductive material which uses the conductive particles; and a connection structure. Each one of conductive particles (1) of the present invention comprises a base particle (2) and a copper-tin layer (3) that is formed on a surface (2a) of the base particle (2). The copper-tin layer (3) contains an alloy of copper and tin. The amount of copper contained in the entire copper-tin layer (3) is more than 20% by weight but not more than 75% by weight, and the amount of tin contained therein is not less than 25% by weight but less than 80% by weight. An anisotropic conductive material of the present invention contains the conductive particles (1) and a binder resin. A connection structure of the present invention comprises a first member to be connected, a second member to be connected, and a connection part that connects the first and second members to be connected. The connection part is formed of the conductive particles (1) or the anisotropic conductive material that contains the conductive particles (1).

Description

201222558 VI. Description of the Invention: [Technical Field] The present invention relates to, for example, an electroconductive particle which can be used for connection between electrodes, and more particularly to a substrate having a substrate and disposed on the substrate Conductive particles of a conductive layer on the surface of the particles. Further, the present invention relates to an anisotropic conductive material and a bonded structure using the above conductive particles. [Prior Art] An anisotropic conductive material such as an anisotropic conductive paste or an anisotropic conductive film is widely known. The anisotropic conductive material is obtained by dispersing conductive particles in a binder resin. The anisotropic conductive material can be used for connection between an IC (Integrated Circuit) wafer and a splicable printed circuit board, and connection of an IC chip to a circuit substrate having an ITO (Indium-Tin Oxide) electrode. Wait. For example, after the anisotropic conductive material is disposed between 1 (the electrode of the wafer and the electrode of the circuit board, heating and pressurization are performed, the electrodes can be electrically connected. As the anisotropic conductive material. An example of the conductive particles to be used is a conductive particle comprising a resin particle and a copper layer provided on the surface of the resin particle, as disclosed in Patent Document 1 below. The embodiment discloses such a conductive particle, but it is described that a good electrical connection can be obtained in connection with a circuit to the circuit. As in the embodiment described in the patent document ,, the previous recording layer is used. The conductive particles are the mainstream. However, nickel itself has a high resistance and it is difficult to reduce the connection resistance. On the other hand, since copper has a lower resistance than 159121.doc 201222558, the connection resistance is lowered. It is advantageous to use as a conductive layer of conductive particles. However, copper has a softer property than nickel, etc. Therefore, the conductive layer formed of steel is too soft, if it is for conductive particles. When a large force is applied, cracks are easily generated in the conductive layer. For example, when the prior conductive particles are used for the connection between the electrodes to obtain a bonded structure, a large crack is generated in the conductive layer. Therefore, there is a case where the electrodes are not reliably connected. Further, as the conductive particles having the conductive layer containing copper, Patent Document 2 below discloses a ternary system of tin, silver, and copper. In the embodiment of Patent Document 2, in order to obtain conductive particles, a tin plating film is formed on the surface of the copper metal particles, and then a silver plating film is formed to be heated to 24 CTC or more. The ternary alloy coating film of tin-silver-copper is formed by thermal diffusion of the metal. The above-mentioned Patent Document 2 discloses that the composition ratio of the composition in the alloy coating of the tin-silver-copper ternary system is 8 锡. ～998% by weight, silver is 〇丨1% by weight, and copper is (M~H) by weight. Specifically, in all the examples of the above Patent Document 2, tin is 96.5 wt% and silver is 3 wt. %, copper is 〇·5 wt% alloy coating The conductive particles contain relatively little silver and copper and contain relatively more tin'. Therefore, the melting point of the ternary alloy coating of tin-silver-copper becomes relatively low, and contains a conductive layer having a lower melting point. When the anisotropic conductive material of the conductive particles is specifically thermocompression bonded to form a connection structure, there is a case where the flow of the conductive layer is caused by heat and the flow is more than necessary. Further, the thickness of the conductive layer connected to the electrode is changed. In the case of a thin connection, there is a case where a connection failure occurs. 159121.doc 201222558 [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-323813 (Patent Document 2) WO2006/080289A1 [Problem to be Solved by the Invention] An object of the present invention is to provide a conductive particle which is less likely to cause a large crack in a conductive layer even if a large force is applied to the conductive particles, and a difference in the use of the conductive particle. A conductive material and a bonded structure. Further, the object of the present invention is to provide an electroconductive particle which can suppress excessive thermal deformation and outflow of a copper-tin layer when the copper-tin layer has a relatively high melting point and is thermocompression bonded to form a bonded structure. And an anisotropic conductive material and a connection structure using the conductive particles. [Technical means for solving the problem] According to a broad aspect of the present invention, there is provided an electroconductive particle comprising a soil material particle and a copper-tin layer containing copper and tin disposed on a surface of the substrate particle and The copper-tin layer contains an alloy of copper and tin, and the content of copper in the copper-tin layer as a whole exceeds 20% by weight/◦ and is 75% by weight or less, and the content of tin 1 is 25% by weight or more and less than 8 〇 Weight 〇 /0. In a specific aspect of the conductive particles of the present invention, the steel-tin layer has a melting point of 550 eC or more. In a specific aspect of the conductive particles of the present invention, the copper in the copper-tin layer as a whole The content is 40% by weight or more and 60% by weight or less, and the content of tin is 40% by weight or more and 6% by weight or less. 15912 丨.doc 201222558 In a particular aspect of the electrically conductive particles of the present invention, the electrically conductive particles have protrusions on the surface. In another aspect of the invention, the conductive material of the invention has an insulating material disposed on the surface of the steel-tin layer. In still another specific aspect of the conductive particles of the present invention, the insulating material is an insulating particle. The anisotropic conductive material of the present invention contains the conductive particles and the binder resin composed according to the present invention. The connection structure of the present invention includes a first connection target member, a second connection target member, and a connection portion that connects the first and second connection target members, and the connection portion is made of conductive particles according to the present invention. It is formed or formed by an anisotropic conductive material containing the conductive particles and the binder resin. [Effects of the Invention] The conductive particles of the present invention have a copper-tin layer containing copper and tin on the surface of the substrate particles, and the copper-tin layer contains an alloy of copper and tin, and the copper-tin layer as a whole The content of copper in the content exceeds 20% by weight and is 75% by weight or less and the content of tin is 25% by weight or more and less than 80% by weight. Therefore, it is difficult to produce a conductive layer even if a large force is applied to the conductive particles. Larger cracks. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described with reference to the specific embodiments and the embodiments of the present invention. Fig. 1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.

159121.doc 201222558 Figure. The electroconductive particle 1 shown in Fig. 1 is provided with a substrate particle 2, and a copper-tin layer 3β steel-tin layer 3 provided on the surface 2a of the substrate particle 2 is a conductive layer (the second layer). The conductive particles i may further include an insulating material disposed on the surface 3a of the copper-tin layer 3. Further, another conductive layer (second conductive layer) such as a layer may be deposited on the surface h of the copper-tin layer 3. The insulating material may be indirectly disposed on the surface 3a of the steel-tin layer 3 by using another conductive layer such as a layer. The copper-tin layer 3 contains an alloy of steel and tin. In the present embodiment, the copper tin layer 3 is a copper/tin alloy layer. Part of the copper-tin layer may also be free of tin, and portions of the copper-tin layer may also be free of copper. For example, the inner portion of the copper-tin layer may also contain only copper, and the outer portion of the copper-tin layer may also contain only tin. The content of copper in the entire copper-tin layer 3 exceeds 2% by weight and is 75% by weight or less, and the content of tin is 25% by weight or more and less than 8% by weight. This embodiment is characterized in that it is provided on the surface of the substrate particle 2. The upper copper-tin layer 3 contains an alloy of copper and tin, and contains copper in the entire copper-tin layer 3. It is more than 20% by weight and is 75% by weight or less, and the content of tin is more than 5% by weight and less than 80% by weight. By forming such a copper-tin layer 3, it is difficult to cause a large crack in the conductive layer even if a large force is applied to the conductive layer. This is considered to be due to the alloying of copper and tin, copper and tin. The hardness of layer 3 is moderately high. Therefore, when the conductive particles 1 are used for the connection between the electrodes to obtain a connection structure, it is difficult to cause a large crack in the conductive layer A, and the conduction reliability between the electrodes can be improved. Further, the above-mentioned large crack is a dream and a sinusoid which guides the degree that the electric layer peels off from the substrate particles and falls off to produce a connection failure between the electrodes of I59121.doc 201222558. Further, the 'copper-tin layer 3 contains a relatively large amount of copper', so that the connection resistance between the electrodes can be lowered. Furthermore, copper is more conductive than recorded. Therefore, in order to improve the conductivity, it is preferable to use copper instead of recording. The present invention is the use of copper in the conductive layer. Further, the present invention uses a relatively large amount of copper unlike the conductive material generally called solder. The content of copper in the entire copper-tin layer 3 is preferably 3% by weight or more, more preferably 35% by weight or more, still more preferably 5% by weight or more, and more preferably 7 Å or more. The content of the knit in the steel-tin layer 3 as a whole is preferably 3% by weight or more, preferably 70% by weight or less, more preferably 65% by weight or less, and still more preferably 60% by weight or less. Preferably, the content of copper in the entire copper-tin layer 3 is 3% by weight or more and 7% by weight or less, and the content of tin is 3 Å by weight or more and 70% by weight or less. More preferably, the content of the steel in the entire copper-tin layer 3 is 35% by weight or more and 65% by weight or less, and the content of tin is 5% by weight or more, and more preferably, the weight of the steel layer is preferably the steel-tin layer 3 The total copper content in the whole is 4 weights and 60 weights. /〇 The following, and the content of tin is 4% by weight or more and 60% by weight or less. In particular, when the content of copper in the entire copper-tin layer 3 is 4% by weight or more and 6% by weight or less, and the content of tin is 40% by weight or more and 6% by weight or less, even if it is conductive. The layer imparts greater force and is more difficult to create larger cracks in the conductive layer. Further, the content of the metal such as copper and tin in the present invention is a value of 159l21.doc 201222558 obtained by weight component of copper or tin relative to the total weight of the metal of the conductive layer. The measurement method is as follows: a metal in which a conductive layer is melted with aqua regia, and a solution in which the metal is dissolved is measured using ICP (Inductively Coupled Piasma) inductively coupled plasma, "ULTIMA2" manufactured by Horiba, Ltd.) The obtained metal ion concentration is used to calculate the weight of the metal of the conductive layer and the amount of each metal. The conductive particles i shown in Fig. 1 can be obtained, for example, by using the conductive particles shown in Fig. 4 . A copper-containing copper layer 52 is formed on the surface 2a of the substrate particle 2. Then, a tin layer 53 containing tin is formed on the surface 52a of the copper layer 52, and conductive particles 51 before heating are obtained. Then, the conductive particles 51 are heated to alloy copper with tin. . In order to efficiently alloy copper and tin, the heating temperature is preferably 150 C or more, more preferably 18 〇 ° C or more, and is preferably 25 Å or less, more preferably 23 〇 ° C or less. In order to efficiently alloy copper with tin, it is particularly preferable to heat the V-electro-particles at 18 to 24 C for 18 to 24 hours. The copper-tin layer 3 is preferably a copper-tin layer which is heat-treated for 15 generations or more in a manner containing an alloy of copper and tin. In the conductive particles 51, the content of copper and the content of tin in the entire copper-tin layer 3 can be adjusted by adjusting the respective thicknesses of the copper layer 52 and the tin layer. The conductive particles of the present invention are preferably conductive particles obtained by heating a conductive layer provided with a copper layer on the surface of the substrate particles and a tin layer on the surface of the copper layer. Fig. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention. The conductive (4) shown in Fig. 2 is provided with a substrate particle 2, and a copper-tin layer 12 provided on the surface 2a of the substrate 159121.doc 201222558 material particle 2 is a conductive layer. Conduction The green particles 11 have a plurality of core materials 13 on the surface 2a of the substrate particles 2. The copper-tin layer 12 as a conductive layer covers the core material 13. The conductive layer is coated with a substance 13 whereby the conductive particles have a plurality of protrusions 14 on the surface 丨丨 & The conductive particles U have a plurality of protrusions 14 on the surface 12& outside the copper-tin layer 12. The protrusions 14 are formed on the surface 12a of the copper-tin layer 12. The surface 12a of the copper _ tin layer 12 is embossed by the core material 13 to form the protrusions 14. A core material 13 is disposed inside the protrusions 14. Other conductive layers such as a palladium layer may be laminated on the surface 12& of the copper-tin layer 12. The conductive particles 11 are provided with insulating particles disposed on the surface 12a of the copper-tin layer 2. The insulating particles 15 are insulating materials. Other conductive layers such as a palladium layer may be present between the copper-tin layer and the insulating particles. In the present embodiment, a part of the surface 12a of the copper-tin layer 12 is covered by the insulating particles I. In this manner, the conductive particles may have insulating particles 15 adhered to the surface of the conductive layer such as a copper-tin layer. However, it is not necessary to provide the insulating particles 15. Further, an insulating resin layer may be provided in addition to the insulating particles 15. The conductive particles may have an insulating resin layer adhered to the surface of a conductive layer such as a copper-tin layer. The surface of the conductive layer such as a copper-tin layer may be coated with an insulating resin layer. This insulating resin layer is an insulating material. In Fig. 5, the conductive particles of the third embodiment of the present invention are shown in cross section. The conductive particles 61 shown in Fig. 5 are provided with a substrate particle 2, a copper-tin layer 3, and a second conductive layer 62. The second conductive layer 62 is provided on the surface 3a of the copper-tin layer 3 in the conductive particles 1. The second conductive layer 62 is different from the copper-tin layer 3, and is also -10- 159121.doc

201222558 A second conductive layer can be provided on the surface 12a of the copper-tin layer 12 in the conductive particles 11. Further, a second conductive layer may be provided on the surface of the substrate particles, and a copper-tin layer may be provided on the second conductive layer. That is, the second conductive layer may be disposed between the substrate particles and the copper-tin layer. In the figure, the cross-sectional graph is not the conductive particles of the fourth embodiment of the present invention. The conductive particles 7 i which are not in the middle include the substrate particles 2 and the copper-tin layer 72 provided on the surface 2a of the substrate particles 2. The steel-tin layer 72 has a second region and a region thinner than the i-th region. The copper-tin layer 72 has a thickness unevenness of 0. The base material particles include resin particles, inorganic particles, organic-inorganic hybrid particles, and metal particles. The substrate particles are preferably resin particles formed of a resin. When the electrodes are connected, the conductive particles are usually placed between the electrodes, and the conductivity is usually made. If the substrate particles are resin particles, the conductive particles are easily deformed by compression. The contact area between the conductive particles and the electrodes Increase. Therefore, the conduction reliability between the electrodes can be improved. As the resin for forming the above resin particles, various organic substances can be preferably used. As a tree for forming the above-mentioned resin particles, for example, polyethylene, polypropylene, polystyrene, polyethylene oxide, polyvinylidene chloride, polypropylene, polyisobutylene, polybutylene, etc. can be used. , acrylic resin such as polymethyl methacrylate, polyacrylic acid f ester, polyalkylene terephthalate, polyfluorene, polycarbonate, polyamide, phenol formaldehyde resin, trimeric murine formaldehyde resin, benzene And guanamine formaldehyde resin, urea formaldehyde resin and the like. Example 159121.doc 201222558 For example, by polymerizing one or more kinds of polymerizable monomers having ethylenic unsaturation &, it is possible to design and synthesize resin particles having physical properties suitable for any compression of a conductive material. . In the case where the monomer having an ethylenically unsaturated group is polymerized to obtain the above resin particles, examples of the monomer having an ethylenically unsaturated group include a non-crosslinkable monomer and a crosslinkable monomer. Examples of the non-crosslinkable monomer include a styrene monomer such as styrene or &methyl styrene, and a carboxyl group such as (mercapto)acrylic acid, cis-dicarboxylic acid, and maleic anhydride. Monomer, methacrylate (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (a Base) lauryl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isofuyl (mercapto) acrylate, etc. (methyl) Alkyl acrylates, oxygenated atoms such as 2-hydroxyethyl (meth)acrylate glyceryl (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate (曱Acrylates, nitrile-containing monomers such as (fluorenyl) acrylonitrile, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, vinyl acetate, vinyl butyrate , vinyl laurate, vinyl stearate and other acid vinyl esters, ethylene, propylene, different An unsaturated hydrocarbon such as pentadiene or butadiene, a trifluorodecyl (meth)acrylate, a pentafluoroethyl (meth)acrylate, a halogen-containing monomer such as ethylene oxide, vinyl fluoride or gas styrene. Examples of the crosslinkable monomer include tetrakis(hydroxy)methanetetrakis(meth)acrylate, tetramethyloldecanetri(meth)acrylate, and tetrahydroxymethylmethanedi(meth)acrylate. Ester, trimethylolpropane tris(mercapto)propene 159121.doc -12-

201222558 Sour vinegar, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, glyceryl tris(decyl) acrylate, glyceryl bis(decyl) acrylate, (poly)ethylene glycol bis ( Multifunctional such as fluorenyl acrylate, (poly)propylene glycol bis(indenyl) acrylate, (poly)bis(meth)acrylic acid tetradecyl methacrylate, 1,4-butanediol di(meth)acrylate (fluorenyl) acrylates, triallyl (iso) cyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, two A monomer containing decane such as allyl ether, 丫_(meth) propylene methoxy propyl trimethoxy decane, trimethoxy fluorenyl phenyl vinyl or vinyl dimethoxy decane. The above resin particles can be obtained by polymerizing the above-mentioned polymerizable monomer having an ethylenically unsaturated group by a known method. As such a method, for example, a method of performing suspension polymerization in the presence of a radical polymerization initiator, and a method of swelling a monomer and a radical polymerization initiator to polymerize non-crosslinked particles are exemplified. . In the case where the substrate particles are inorganic particles or organic-inorganic hybrid particles, the inorganic material used to form the substrate particles may be, for example, sulphur dioxide or black. The particles formed by the above-mentioned dioxotomy are not particularly limited, and examples thereof include hydrolysis of a compound having two or more hydrolyzable anthracene groups to form crosslinked polymer particles: obtained particles. In the case of the metal particles, the metal particles are used as the metal particles to form the metal pull, and silver 3 ruthenium, gold, titanium, and the like are exemplified. However, it is preferred that the substrate particles are not metal particles. The average particle diameter of the substrate particles is preferably in the range of 100 Å. If the average particle diameter of the substrate particles is 1 μηι or more, the conductivity between the electrodes can be further improved. When the average particle diameter of the substrate particles is 10 0 μm or less, the interval between the electrodes can be narrowed. The average particle diameter of the substrate particles is preferably 2 μΠ1, more preferably 50 μηι, further preferably 30 μηη, and particularly preferably 5 μηι. The above average particle diameter represents a number average particle diameter. The average particle diameter can be measured, for example, by using a Coulter a ten-number device (manufactured by Beckman C〇uher Co., Ltd.). The outer surface of the steel-tin layer may be a smooth spherical shape, and the outer surface may be elongated in the form of irregularities formed by scaly or plate-shaped metal pieces, and the copper-tin layer may be single. The conductive layer of the layer may also be a conductive layer laminated with a plurality of layers of scaly or plate-like conductive material. The Vickers hardness (four) of the copper/tin layer is preferably 1 GG or more, preferably 500 or less. 1 The Vickers hardness of the copper/tin layer is less than or equal to the lower limit and less than the upper limit, and it is more difficult to produce cracks in the conductive layer. Moreover, the conduction reliability in the connection structure is further improved. The copper-tin layer has a melting point of more than L, and a horse is 55 〇c or more, more preferably 00 (TC or more. The upper limit of the steel-tin layer is not particularly limited. The copper is thermally deformed and (4). On, it can suppress the excessive copper and tin layers.

The melting point of == is the value measured by Dsc (differential scanning calorimetry, SII EXSTARX tearing). The copper-tin layer may have a second region. The steel-tin layer 2 and the thickness thinner than the first region may be U times or more, and the thickness may exceed 1 ' of the minimum thickness, may be 1.5 times or more, or may be 2 times to I5912I.doc

• 14_ S 201222558 When the thickness of the steel-tin layer is not uniform, when the connecting structure is obtained by using an anisotropic conductive material containing conductive particles and a binder resin, the conductive particles and the electrode are effectively removed. Adhesive resin. Therefore, the conduction reliability in the obtained connection structure is improved. Further, by forming the copper-tin layer by the following physical or mechanical mixing method, it is easy to increase the thickness unevenness. The average thickness of the above copper-tin layer is preferably in the range of 10 to 1000 nm. A lower limit of the average thickness of the copper-tin layer is 2 〇 nm, and more preferably 50 nm. The upper limit is _ nm, and the upper limit is preferably 5 (9) (10), and the upper limit is preferably 3 〇〇 nm. When the average thickness of the copper-tin layer is at least the above lower limit, the conductivity of the conductive particles can be further improved. When the average thickness of the copper-tin layer is less than or equal to the above upper limit, the difference in thermal expansion coefficient between the substrate particles and the copper-tin layer is small, and the copper-tin layer is difficult to peel off from the substrate particles. A method of forming a copper layer on the surface of the substrate particles in order to form the copper-tin layer includes a method of forming a copper layer by electroless deposition, and a method of forming a copper layer by electricity money. . As a method of forming a tin layer on the surface of, for example, a copper layer in order to form a copper-tin layer, there may be mentioned a method of forming a tin layer by electroless ore plating, a method of forming a tin layer by an electric clock, and the like. Further, as a preferred method of forming the above-mentioned copper-tin layer, a physical or mechanical formation method may be used, or a physical or mechanical mixing method may be used. In the physical or mechanical mixing method, mixers, etc. The steel-tin layer may contain genus insofar as it does not inhibit the gold of the present invention other than copper and tin. As the other gold 4, for example, it can be listed as 159121.doc 201222558. Gold, silver, palladium, platinum, palladium, zinc, iron, lead, aluminum, cobalt, indium 'nickel, chromium, titanium, lanthanum, cerium, lanthanum, cerium , cadmium, tungsten, antimony and tin-doped indium telluride (1 butyl) and so on. When the copper-tin layer contains the other metal, the content of the other metal in the copper-tin layer as a whole is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 5 parts by weight. Below %, especially below Si% by weight. The conductive particles may have the second conductive layer. The second conductive layer is a conductive layer different from the copper-tin layer. The second conductive 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 palladium layer or a gold layer, and further preferably a palladium layer. Preferably, the second conductive layer is provided on the surface of the copper-tin layer. The average thickness of the second conductive layer is preferably 5 or more. When the average thickness of the second conductive layer is 5 nnm or more, the second conductive layer is easily formed to be uniformly coated. When the second conductive layer is provided on the surface of the copper-tin layer, the resistance of the conductive particles to the external environment is improved. 'The copper-tin layer is hard to be oxidized, and it is difficult to cause copper and copper in the copper-tin layer. The corrosion of the steel caused by the japany reaction between the metals (materials) constituting the second conductive layer can further improve the electrical conductivity of the entire conductive layer of the conductive particles. The average thickness of the second conductive layer is preferably 5 〇〇 (10) or less. When the average thickness of the second conductive layer is _(10) or less, the cost of the conductive particles is lowered. Further, the amount of metal constituting the second conductive layer can be reduced, so that the environmental load can be reduced. 159121.doc

S •16- 201222558 The lower limit of the average thickness of the above-mentioned layer is 丨〇, and the upper PF is 400 nm. The average thickness of the right layer is 1〇ηηη or more, which can further improve the conductivity of the conductive particles. . The conductive particles of the present invention preferably have protrusions on the surface as in the case of the conductive particles 11. The Vickers hardness (Hv) of the copper-tin layer is preferably 1 Å or more, and it is preferred that the conductive particles have protrusions on the surface. The conductive particles preferably have protrusions on the surface of the conductive layer, and further preferably have protrusions on the surface of the steel-tin layer or the second conductive layer (palladium layer or the like). The above protrusions are preferably plural. In many cases, an oxide film is formed on the surface of the electrode to which the conductive particles are connected. In the case where conductive particles having protrusions are used, the above-described oxide coating m is effectively removed by the protrusions by arranging and pressing the conductive particles between the electrodes. Since &, the electrode can be more reliably brought into contact with the conductive layer of the conductive particles, and the connection resistance between the electrodes can be reduced. Further, when the conductive particles are provided with an insulating material f (an insulating resin layer or an insulating particle or the like) on the surface, or when the conductive particles are dispersed in a resin and used as an anisotropic conductive material, From the protrusion of the conductive particles, the resin H between the conductive particles and the electrode can be effectively removed, and the conduction reliability between the electrodes can be improved. The method of forming a protrusion on the surface of the conductive particle includes a method of forming a conductive layer by electroless ore deposition after attaching a core substance to a surface of the substrate particle, and a method of forming a conductive layer by electroless plating; After the surface of the base particle forms a conductive layer, the core material is adhered, and a method of forming a conductive layer by electroless ore is used as a method of attaching the core substance to the surface of the substrate particle, for example, 159l21.doc 17 201222558: a method of adding a conductive material to be a core material to a dispersion of a substrate particle, and concentrating and adhering the core material to the surface of the particle by, for example, van der Waals force; In the container, a method of adhering the core material to the surface of the substrate particles by a mechanical action such as rotation of the container is added to the conductive material which is a core material. Further, in order to easily control the amount of the core material to be attached, a method of collecting the core material and adhering it to the surface of the substrate particles in the knife solution is preferred. Examples of the conductive material f constituting the core material include conductive oxides such as metal oxides and graphite, and conductive polymerization. Examples of the conductive polymer include a polyethylene block and the like. Among them, conductivity is preferred, and metal is preferred. As the above-mentioned metal, for example, gold, silver, steel, zinc, iron, iron, aluminum, australis, indium, bismuth, bismuth, titanium, strontium, strontium, strontium, and cadmium may be mentioned. = an alloy composed of two or more types of metals, such as a tin alloy, a tin-steel alloy, a tin-silver alloy, and a tin-silver alloy. Among them, more than =, silver or gold. The metal constituting the core material may be the same as or different from the metal constituting the upper electric layer. Further, examples of the compound include oxidation, sulphur dioxide, and oxidation. As the conductive particles U, the conductive particles of the present invention are preferably an insulating material placed on the surface of the above-mentioned steel-tin layer or palladium sound-matching layer. In this case, conductive particles are used for the short circuit between the electrodes. Specifically, when the contact is connected, there is an absolute % between the plurality of electrodes, and a short circuit between the adjacent electrodes is not a short circuit between the upper and lower electrodes: 15912I.doc

-18-201222558 In the case of the connection between the electrodes, the insulating layer between the conductive layer of the conductive particles and the electrode can be easily removed by pressing the conductive particles with two electrodes. When the conductive particles have protrusions on the surface of the palladium layer, the insulating material between the conductive layers of the conductive particles and the electrodes can be removed more easily. The insulating material is preferably an insulating resin layer or insulating particles. The insulating particles are preferably insulating resin particles. Specific examples of the insulating material include polyolefins, (mercapto) acrylate polymers, (mercapto) acrylate copolymers, block polymers, thermoplastic resins, crosslinked products of thermoplastic resins, and heat. A curable resin, a water-soluble resin, and the like. Examples of the polyolefins include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylate copolymer. Examples of the above (fluorenyl) acrylate polymer include poly(methyl) acrylate, poly(meth) acrylate, and poly(decyl) butyl acrylate. Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB (Styrene® Butadien) type styrene-butadiene block copolymer, and SBS (Styrene- Butadien-Styrene, styrene-butadiene-styrene type styrene-butadiene block copolymer, and such hydrides and the like. Examples of the thermoplastic resin include an ethylene polymer and an ethylene copolymer. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and a melamine resin. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polypropylene decylamine, polyvinylpyrrolidone, polyethylene oxide, and methyl cellulose. The conductive particles of the present invention more preferably have insulating particles attached to the surface of the conductive layer. In this case, if the conductive 159121.doc •19-201222558 particles are used for the connection between the electrodes, not only the short circuit between the adjacent electrodes in the lateral direction can be further prevented, but also the connection can be further lowered. The connection resistance between the electrodes. As a method of attaching the insulating particles to the surface of the above-mentioned conductive layer, a chemical method, a physical or mechanical method, or the like can be given. As the above-mentioned chemical method, for example, as described in WO 2003/25955 A1, the insulating particles are attached to the conductive layer of the metal surface particles by a flocculation method using a van der Waals force or an electrostatic force. Further, as the physical or mechanical method, the above-mentioned physical or mechanical method may, for example, be a spray drying method, a mixing method, an electrostatic adhesion method, a spray method, a dip plating method, or a vacuum vapor deposition method. Among them, in the case where the insulating material is hard to be separated, it is preferred to adhere the insulating material to the surface of the conductive layer via chemical bonding. The particle diameter of the insulating particles is preferably 1/5 or less of the particle diameter of the conductive particles. In this case, the particle diameter of the insulating particles is not excessively large, and the electrical connection of the conductive layers is more surely achieved. When the particle diameter of the insulating particles is 1/5 or less of the particle diameter of the conductive particles, when the insulating particles are adhered by the flocculation method, the insulating particles can be efficiently adsorbed on the surface of the conductive particles. on. Further, the particle diameter of the insulating particles is preferably 5 nm or more, more preferably 10 nm or more, more preferably 1000 nm or less, still more preferably 5 Å nm & When the particle diameter of the insulating particles is at least the above lower limit, the distance between adjacent conductive particles is increased as compared with the jumping distance of electrons, and it is difficult to cause leakage. When the particle diameter of the insulating particles is not more than the above upper limit, the pressure and heat required for thermocompression bonding are reduced.

159121.doc S 201222558 The cv (coefficient of variation) value of the particle diameter of the insulating particles is preferably 20% or less. When the cv value is 2% or less, the thickness of the coating layer of the conductive particles becomes uniform, and when the electrodes are thermocompression-bonded, pressure is uniformly applied, and conduction failure is less likely to occur. Further, the CV value of the above particle diameter is calculated by the following formula. C V value (%) of the particle diameter = standard deviation of the particle diameter / average particle diameter x 丨〇〇 For the particle enthalpy distribution, the surface of the coated metal surface can be measured by a particle size distribution meter or the like. SEM can be used after coating (scanning electronic

Microscope, scanning electron microscope) image analysis and the like are measured. Further, in order to expose the conductive layer of the conductive particles, the coverage of the insulating material is preferably 5% or more, preferably 70% or less. The coverage of the insulating material is such that the portion covered with the insulating material accounts for the entire area of the surface area of the metal surface particles. When the coverage is 5% or more, the adjacent conductive particles are more reliably insulated by the insulating material. When the coverage is 70% or less, it is not necessary to apply more than necessary heat and pressure to the connection of the electrodes, and the deterioration of the properties of the adhesive resin caused by the removed insulating material is suppressed. The insulating particles are not particularly limited, and known inorganic particles and organic polymer particles can be used. Examples of the inorganic particles include insulating inorganic particles such as oxidized, cerium oxide and cerium oxide. The organic polymer particles are preferably resin particles obtained by (co)polymerizing one or two or more monomers having an unsaturated double bond. Examples of the monomer having an unsaturated double bond include (meth)acrylic acid, (meth)acrylic acid 159121.doc •21 - 201222558 methyl ester, ethyl (meth)acrylate, and propyl (meth)acrylate. , (butyl) (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, tetramethylol methane tetra(meth)acrylate, trimethylolpropane tri Mercapto) acrylate, tris(meth)acrylate, (poly)ethylene glycol di(decyl)acrylate, (poly)propylene glycol bis(indenyl)acrylate, anthracene, 4-butanediol- (Methyl) acrylic acid vinegar and the like (methyl) acrylic acid S, class of ethylene sulfonium, ethylene ethoxide, styrene, styrene and other styrene compounds. Among them, (fluorenyl) acrylates can be preferably used. The insulating particles preferably have a polar functional group for the conductive layer 'adhering to the conductive particles by the flocculation. Examples of the polar functional group include an ammonium group, a fluorenyl group, a phosphoric acid group, and a hydroxydecyl group. The above polar functional group can be introduced by copolymerizing a monomer having the above polar functional group and an unsaturated double bond. Examples of the monomer having the above ammonium group include N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminopropyl acrylamide, and N,N,N-trimethyl·A. Acryloxyethyl ammonium chloride or the like. Examples of the monomer having the above mercapto group include phenyl dimethyl hydrazine methyl sulfate methacrylate. Examples of the monomer having the above-mentioned phosphoric acid group include acidic phosphatidylphosphonium oxychloride 曰 性 性 甲基 methyl methoxy methoxy methoxy ethoxy propyl acrylate, acidic phosphonium oxy ethoxylated monomethyl group A propylene g-line and an acid-filled oxy-polyoxypropylene alcohol monomethyl acrylate vinegar and the like. Examples of the monomer having the above hydroxyalkylalkyl group include ethylene trihydroxy decane and 3-methacryloxypropyl trihydroxy decane. As another method of introducing the polar functional I to the surface of the insulating particles, a self-based initiator having a polar group is used as a single one having the unsaturated double bond of the above 159121.doc -22-201222558. A method of starting a reagent during bulk polymerization. As the above-mentioned radical initiator, for example, 2,21-azobis{2_methyl-hydroxybutyl]]-propanamine}, 2,2,_azobis[2_(2_淋_2_基)丙院] and 2,2-azobis(2-mercaptopropene) and the salts thereof. (Anisotropic conductive material) The anisotropic conductive material of the present invention contains the above-mentioned conductive particles and a binder resin. The above binder 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 adhesive resin may be used alone or in combination of two or more. Examples of the vinyl resin include a vinyl acetate resin, an acrylic resin, and a styrene resin. The thermoplastic resin may, for example, be a polyanthracene resin, a vinyl acetate, an ethylene acetate copolymer or a polyamide resin. Examples of the curable resin include an epoxy resin, an aminoguanidine Sg tree, a polyimide resin, and an unsaturated polyester resin. Further, 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 above thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-stupidene block copolymer, and a styrene-butadiene-styrene block. a hydride of a segment copolymer and a hydride of a stupid ethylene-isoprene-styrene block copolymer. Examples of the above-mentioned + elastomer include styrene-butadiene copolymer rubber and propylene guess-styrene block copolymer rubber. 15912l.doc -23· 201222558 The anisotropic conductive material may contain, for example, a filler, a bulking agent, a softener, a plasticizer, a polymerization catalyst, and a hardening catalyst, in addition to the conductive particles and the above-mentioned binder resin. Various additives such as coloring agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, and flame retardants. The method of dispersing the above-mentioned conductive particles + in the above-mentioned binder resin is not particularly limited. A previously known dispersion method can be used. In the method of dispersing the above-mentioned conductive particles in the above-mentioned binder resin, for example, a method in which the conductive particles are added to the binder resin and then kneaded by a planetary mixer or the like is dispersed, and a homogenizer or the like is used. a method in which the conductive particles are uniformly dispersed in water or an organic solvent, and then added to the binder resin and kneaded by a star mixer or the like to be dispersed; and the above is carried out with water or an organic solvent. After the binder resin is diluted, the conductive particles are added, and a method such as a sagittal mixer or the like is carried out to disperse the particles. The anisotropic material (4) of the present invention can be (iv) anisotropic conductive I* and an anisotropic conductive film. When the anisotropic conductive material of the present invention is an anisotropic conductive film, it may be a film of an anisotropic conductive layer containing conductive particles other than the conductive particles. The above-mentioned anisotropic conductive material is preferably a secondary conductive paste from the viewpoint of suppressing generation of voids in the joint portion in the joined structure and further improving the reliability of conduction. The anisotropic conductive material is preferably an anisotropic conductive sound and is applied to the upper surface of the member to be joined in a paste state. In the above-mentioned anisotropic conductive material (10% by weight), the above adhesive resin is 159121.doc

-24- 201222558 The amount is preferably in the range of 10 to 99.99% by weight. The above binder resin is contained. More preferably, the P 艮 is 3 〇 weighs 4%, the (9) preferred lower limit is 5 〇 wt%, the lower limit is preferably 7 〇 wt%, and the more preferred upper limit is 99 9% by weight. When the content of the above-mentioned binder resin satisfies the above lower limit and upper limit, the conductive particles can be effectively disposed between the electrodes, and the conduction reliability between the electrodes can be improved step by step. The content of the conductive particles is preferably in the range of 〇1 to 2% by weight based on 1% by weight of the anisotropic conductive material. A more preferable lower limit of 3 of the above conductive particles is 〇丨% by weight, and even more preferably, the upper limit is 1% by weight. When the content of the conductive particles satisfies the above lower limit and upper limit, the conduction reliability between the electrodes can be further improved. (Connection structure) The connection structure member can be connected by using the t conductive particles + or the anisotropic conductive material containing the conductive particles and the binder resin, whereby a connection structure can be obtained. Preferably, the connection structure includes a second connection target member, a second connection target member, and a connection portion that connects the first and second connection target members, and the connection portion is formed by the conductive particles (four) of the present invention. Or by the inclusion of the conductive particles and the adhesive resin (4) (four) material (four). In the case of using conductive particles, the connecting portion itself is a conductive particle. In other words, the first and second connection target members are connected by conductive particles. Fig. 3 is a front 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 an i-th connection target member, a second 159121.doc • 25 201222558 connection target member 23, and a connection portion 24 that connects the second and second connection object members 22 and 23. It is formed by hardening an anisotropic conductive material containing conductive particles. Further, in Fig. 3, the conductive particles 丨 are shown in a schematic form for convenience of illustration. In addition to the conductive particles 1, conductive particles 11, 61, and 71 can also be used. The first connection member 22 has a plurality of electrodes 22b on the upper surface 22a. The second connection member 23 has a plurality of electrodes on the lower surface, and the electrodes 22b and 23b are electrically connected by one or a plurality of conductive particles j. Therefore, the first 'second connection target members 22 and 23 are electrically connected by the conductive particles 1. The method for producing the above-described connection structure is not particularly limited. The production example of the connection structure is a method in which the anisotropic conductive material is placed between the second connection target member and the second connection target member to obtain a laminate, and the laminate is heated and pressurized. The pressure of the above pressurization is about 9.8 x l 〇 4 to 4.9 x l 〇 6 pa. The heating temperature is about 120 to 22 (about TC. By using the conductive particles of the present invention, even if such a pressure is applied, it is difficult to cause a large crack in the copper-tin layer. Therefore, the conduction between the electrodes can be improved. Specific examples of the connection target member 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. Examples of the electrode include a metal electrode such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode. The connection target member is a flexible printed substrate 159121.doc •26-201222558 When the electrode is a glass substrate, the electrode is preferably an aluminum electrode, a steel electrode, a molybdenum electrode or a tungsten electrode. In the above electrode, the electrode may be an electrode formed only by (4), or may be a layer of a layer on the surface of the i-metal oxide layer. Examples of the metal oxides 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, A1, and ruthenium. When other forms of use of the conductive particles of the present invention are listed, conductive particles may be used as a conductive material for electrically connecting the upper and lower substrates of the liquid crystal display element. The conductive particles may be mixed and dispersed. a thermosetting resin or a thermal uv (ultraviolet), which is applied to a single-sided substrate in a punctiform manner and bonded to a counter substrate; and the conductive particles are mixed and dispersed. In the peripheral sealant, the method is applied in a linear form to serve as a method for electrically connecting the sealing strip and the upper and lower substrates, etc. The conductive particles of the present invention can be applied to any of the above-described forms of use. Since the conductive particles are provided with a conductive layer on the surface of the substrate particles, the substrate particles can be electrically connected without being damaged by the excellent elasticity of the substrate particles. The present invention will be specifically described by way of examples and comparative examples. The present invention is not limited to the following examples. (Example 1) (1) Resin particle formation step in containing 3% by weight of polyvinyl alcohol (Japan Synthetic Chemical Industry) Adding 2 parts by weight of divinylbenzene, 3 parts by weight of trimethylolpropane trimethacrylate, and benzoyl peroxide to 800 parts by weight of an aqueous solution of GH21" 2012 manufactured by the company 159121.doc -27-201222558) 2 parts by weight of formazan, stirred and mixed, and heated to 80 ° C while stirring in a nitrogen atmosphere, and reacted for 15 hours to obtain resin particles. The obtained resin particles were washed with distilled water and decyl alcohol, and then subjected to washing. Separation operation was carried out to obtain resin particles having an average particle diameter of 4.1 μm and a coefficient of variation of 5.% by weight. Hereinafter, there is a case where it is referred to as a resin particle enthalpy. (2) Electroless copper plating step The obtained resin particles A 10 g were subjected to a button etching treatment and then washed with water. Then, palladium sulfate is added to the resin particles to adsorb the ions on the resin particles. Then, the resin particles which adsorb the cation ions are added to the aqueous solution containing 5% by weight of dimethylamine borane to activate the palladium. To the resin particles, distilled water of 5,000 m L and 4 vines of a particle suspension were added. 'Prepare to prepare 40 g/L copper sulfate (5 hydrate), 1 〇〇g/L ethylenediaminetetraacetic acid (EDTA 'Ethylene Diamine Tetra-acetic Acid), 50 g/L sodium gluconate, and 25 g / L of formaldehyde and adjusted. It is a non-electrolytic bond solution with a pH of 10.5. The electroless plating solution was gradually added to the above-mentioned particle suspension and subjected to electroless copper plating while stirring at 50 ° C. In this manner, a steel layer (thickness of about 40 nm) was provided on the surface. Copper-plated particles (3) Electroless tin plating step A solution containing 5 g of vaporized tin and 1 mL of ion-exchanged water was prepared, and 15 g of the obtained copper-plated particles were mixed to obtain an aqueous suspension. A plating solution was obtained by adding 30 g of thiourea and 80 g of tartaric acid to the aqueous suspension. The plating 159121.doc -28 -

The 201222558 solution was set to a bath temperature of 60 ° C and reacted for 20 minutes. Further, in the plating solution, 20 g of vaporized tin 20 g of citric acid and 30 g of sodium hydroxide were further added, and the mixture was reacted at a bath temperature of 6 (TC for 20 minutes, thereby obtaining tin on the surface of the copper layer. Particles of a layer (having a thickness of about 72 nm) (4) Alloying step The particles provided with the tin layer on the surface of the copper layer were heated at 220 ° C for 20 hours. After heating, the copper and the tin layer were alloyed. In this manner, a conductive particle in which a copper-tin layer (having a thickness of about 1 Å) is provided on the surface of the resin particle and the copper-tin layer contains an alloy of copper and tin is obtained. In the middle, the content of steel and tin contained in the copper-tin layer as a whole was subjected to δ parity, and as a result, the content of copper was 40% by weight, and the content of tin was 6% by weight. (Example 2) Electroless copper plating In the step, the thickness of the copper layer was set to about 5 Å, and the thickness of the tin layer was changed to about 6 Å in the electroless tin plating step, and the resin particles were obtained in the same manner as in Example 1. a copper-tin layer (having a thickness of about 1 〇〇 nm) on the surface and the copper-tin layer containing an electroconductive grain of an alloy of copper and tin The content of copper and tin contained in the entire copper-tin layer was evaluated for the obtained conductive particles, and as a result, the content of steel was 5 Å by weight, and the content of tin was 50% by weight/〇. 3) ------------ _ ~ / 砹 约 00 nm, and in the electroless tin plating step to change the thickness of the tin layer to about 48 nm, in addition to implementation In the same manner as in Example 1, 159121.doc -29-201222558 having a copper-tin layer (thickness about loo nm) and the copper-tin layer containing conductive particles of steel and tin human gold was obtained in the same manner as in Example 1. The conductive particles obtained were evaluated for the content of copper and tin contained in the entire steel layer, and as a result, the content of steel was 60% by weight and the content of tin was 40% by weight. (Example 4) (1) Core substance adhesion step After etching the resin particles A 10 g obtained in Example 1,

Washed with water. Then, sulfuric acid was added to the resin particles, and the particles were adsorbed on the resin particles. D The resin particles having palladium adhered thereto were dispersed in 300 mL of ion-exchanged water for 3 minutes to be dispersed to obtain a dispersion. Then, metal nickel particles ("2020SUS" manufactured by Mitsui Metals Co., Ltd., average granules 2 〇〇 nm) 1 g were added to the above dispersion liquid for 3 minutes to obtain resin particles to which the core material was attached. / (2) Preparation of Conductive Particles The electroless copper plating step, the electroless tin plating step, and the alloying step were carried out in the same manner as in Example except that the resin particles having the core material adhered thereto were used to obtain the resin particles. A copper-tin layer is provided on the surface, and the steel-tin layer contains conductive particles of an alloy of copper and tin. The obtained conductive particles have protrusions on the surface of the copper-tin layer. The content of copper and tin contained in the entire steel-tin layer was evaluated for the obtained conductive particles, and as a result, the content of copper was 40% by weight and the content of tin was 60% by weight. Further, when the content of copper and tin is sought, "the nickel contained as a core material is excluded. (Example 5) 159121.doc 201222558 The resin particle A was changed to a copolymer resin particle of 1,4-butanediol diacrylate and tetramethyl methacrylate tetraacetic acid S (1,4-di Conductivity was obtained in the same manner as in Example 4 except that the alcohol dipropylene acid was used: tetrahydroxymethane methane tetraacrylate = 95% by weight: 5% by weight, which is referred to as the case of the resin particles B. particle. The obtained conductive particles have protrusions on the surface of the copper-tin layer. (Example 6) (1) The insulating resin particles were prepared in a separable flask of 1000 mL equipped with four separable masks, stirring blades, three-way cocks, cooling tubes and temperature probes. Ethyl decyl acrylate 100 mmol, N, N, N-trimethyl-N-2-mercaptopropyl methoxyethyl ammonium chloride 1 mmol, and 2,2'-azobis (2-lung 1 mmol of the monomer composition of the propane) dihydrochloride was added to the ion exchange water so that the solid content was 5 wt%, and then stirred at 2 rpm and at 70 ° C under a nitrogen atmosphere. The polymerization was carried out for 24 hours. After completion of the reaction, the mixture was cooled to obtain an insulating resin particle having an ammonium group, an average particle diameter of 22 〇 nm, and a cV value of 10% on the surface. The insulating resin particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain an aqueous dispersion of 1% by weight of the insulating resin particles. The conductive particles 1 〇 g obtained in Example 5 were dispersed in xenotypes of ion-exchanged water 500, and 4 g of an aqueous dispersion of insulating resin particles was added, and the mixture was stirred at a temperature for 6 hours. After filtering with a 3 μηη mesh filter, the mixture was washed with methanol and dried to obtain conductive particles to which insulating resin particles were adhered. 159121.doc -31 - 201222558 Observation by a scanning electron microscope (SEM) revealed that only one coating layer of insulating resin particles was formed on the surface of the conductive particles. The coverage area of the insulating resin particles (i.e., the projected area of the grain size of the insulating resin particles) with respect to the area of 2.5 μm from the center of the conductive particles was calculated by image analysis, and the coverage was 30%. (Example 7) Conductive particles were obtained in the same manner as in Example 1 except that the resin particles were changed to resin particles. (Example 8) Conductive particles having insulating resin particles adhered thereto were obtained in the same manner as in Example 6 except that the conductive particles obtained in Example 5 were changed to the conductive particles obtained in Example 。. (Example 9) Conductive particles to which insulating resin particles were attached were obtained in the same manner as in Example 6 except that the conductive particles obtained in Example 5 were changed to the conductive particles obtained in Example 4. . (Example 10) In addition to the conductive particles obtained in Example 7 obtained in Example 5, the conductive particles obtained in Example 7 were obtained in the same manner as in Example 6 Conductive particles of resin particles. (Example 11) Using the conductive particles The conductive particles obtained in Example 1 were prepared to carry out the following steps (1) and (2). (1) Electroless palladium plating step 159121.doc -32· 201222558 The obtained copper plating particles 丨0 g were dispersed in 500 mL of ion-exchanged water using an ultrasonic processor to obtain a particle suspension. Further, a non-electrolytic solution containing 4 g/L of palladium sulfate (anhydride), 2.4 g/L of ethylenediamine, 4.0 g/L of barium sulfate, and 35 g/L of sodium hypophosphite and adjusted to pH 1 was prepared. Plating solution "The above-mentioned non-electrolytic rhodium plating solution was gradually added while stirring the above-mentioned particle suspension at 5 Torr < t, and electroless palladium plating was performed. The amount of the electroless plating solution added was adjusted so that the thickness of the palladium layer became 1 〇 nm. The obtained resin particles of the ore were washed with distilled water and methanol, and then vacuum dried. In this manner, conductive particles having a copper layer on the surface of the resin particles and a palladium layer on the surface of the copper layer were obtained. (2) The milk washing removal step is performed by dispersing 1 g of the obtained conductive particles in 1000 mL of distilled water (specific resistance of 18 Μ Ω), charging into an autoclave with a stirrer and under pressure of 〇i Mpa, The mixture was washed with stirring at 121 ° C for 10 hours. Thereafter, it was filtered and dried. In this manner, a copper-tin layer (having a thickness of about 100 nm) is provided on the surface of the resin particle, and the copper-tin layer contains an alloy of copper and tin, and palladium is further provided on the surface of the copper-tin layer. Conductive particles of a layer (having a thickness of 1 〇 nm). (Example 12) The resin particles Αβ obtained in Example 1 were prepared, and copper powder (particle diameter: 3_0 to 7.0 μηι) and tin powder (particle diameter: 3 〇 to 7 〇 μιη) were prepared. Using resin particles A, copper powder, and tin powder, using a mixer (manufactured by Nara Machinery Co., Ltd.) and obtaining a copper on the surface of the resin particles by physical/mechanical mixing method, 159121.doc -33 - 201222558 - Particles of the tin layer (thickness 10〇11111). Then, the particles having the steel-tin layer obtained on the surface of the resin particles were heated at 220 C for 20 hours. After heating, the steel is alloyed with the tin layer. In this manner, conductive particles in which a copper-tin layer (thickness: 100 nm) was provided on the surface of the resin particles and the copper-tin layer contained an alloy of copper and tin were obtained. = The content of copper and tin contained in the entire copper-tin layer was evaluated for the obtained conductive particles, and as a result, the content of copper was 40% by weight and the content of tin was 6% by weight. The maximum thickness of the above copper-tin layer is more than twice the minimum thickness. (Example 13) The resin particles A used in Example 1 were prepared. Further, a copper-tin alloy powder (copper content of 40% by weight, tin content of 6% by weight, and particle diameter of 3,000 to 7.5 μm) was prepared. Using a resin particle crucible and a copper-tin alloy powder, a copper-tin layer (thickness 1 Å) was obtained on the surface of the sapphire particles by a mixer (manufactured by Nara Machinery Co., Ltd.) and by physical/mechanical mixing. 〇nm) particles. With respect to the obtained conductive particles, the content of copper and tin contained in the entire copper-tin layer was evaluated. As a result, the content of copper was 4% by weight and the content of tin was 6 Å by weight. /. . The maximum thickness of the above copper-tin layer is more than twice the minimum thickness. (Comparative Example 1) The resin particles A obtained in Example 1 were prepared. The resin particles A J 〇 g were subjected to an etching treatment and then washed with water. Then, sulfuric acid is added to the resin particles to adsorb palladium ions to the resin particles. Then, an adsorption solution of 159 l 2 l.doc • 34 · 201222558 was added to an aqueous solution containing 0.5% by weight of diammonium borane to activate the resin particles. 500 mL of distilled water was added to the resin particles to obtain a particle suspension. Further, prepare 40 g/L of copper sulfate (5 hydrate), 1 〇〇g/L of ethylenediaminetetraacetic acid (EDTA) '50 g/L of gluconic acid and 25 g/L of jun Adjusted. An electroless plating solution with a pH of 10.5. The above electroless plating solution was gradually added to the above-mentioned particle suspension, and electroless copper plating was carried out while stirring at 50 °C. In this way, copper particles (conductive particles) provided with a copper layer (thickness 1 〇〇 nm) on the surface were obtained. In Comparative Example 1, no tin layer was provided on the surface of the copper layer. (Comparative Example 2) The particles having no tin layer (thickness: about 72 nm) on the surface of the copper layer (thickness: about 40 nm) obtained after the electroless tin plating step of Example 1 were used as the conductive particles. The alloying step was not carried out in Comparative Example 2. (Comparative Example 3) The thickness of the copper layer was set to be about 8 Å in the electroless copper plating step, and the thickness of the tin layer was changed to about 2 Å (four) in the electroless tin plating step, and other methods were carried out. In the same manner as in Example 1, a conductive layer in which a copper tin layer (thickness: 100 nm) was provided on the surface of the resin particle and the copper-tin layer contained an alloy of copper and tin was obtained. With respect to the obtained conductive particles, the content of copper and tin contained in the entire copper/tin layer t was evaluated, and the content of copper was 8 Å by weight and the content of tin was 20% by weight. Comparative Example 4) 14 nm, and in nm, in addition to the electroless copper plating step A, the thickness of the copper layer is set to about the thickness of the tin layer in the electroless tin plating step to about % 159121.doc • 35· In the same manner as in Example 1, a conductive particle in which a copper-tin layer (thickness: about 100 nm) was provided on the surface of the resin particle and the copper-tin layer contained an alloy of copper and tin was obtained in the same manner as in Example 1. The conductive particles were evaluated for the content of copper and tin contained in the entire copper-tin layer, and as a result, the content of copper was 15% by weight and the content of tin was 85% by weight. (Example 14) In the electroless copper plating step The thickness of the copper layer was set to about 3 〇 nm, and the thickness of the tin layer was changed to about 84 nm in the electroless tin plating step, except that the surface of the resin particle was provided in the same manner as in Example 1. a copper tin layer (having a thickness of about 1 〇〇 nm) and the copper-tin layer contains a guide of an alloy of copper and tin For the obtained conductive particles, the content of copper and tin contained in the entire copper-tin layer was evaluated, and as a result, the content of copper was 3% by weight and the content of tin was 70% by weight. (Evaluation) (1) ) The crack of the conductive layer is prepared by forming a copper substrate having a copper electrode having an L/S of 1 μm η/ιοο μηι. Further, an epoxy resin containing 10 parts by weight of conductive particles as a binder resin (manufactured by Mitsui Chemicals Co., Ltd.) is prepared. Rsturct B〇nd χΝ_5Α") 85 parts by weight, and an imidazole type hardener 5 parts by weight of an anisotropic conductive paste. After the conductive particles are contacted with the copper electrode, the counter-conductive conductive paste is applied to the upper surface of the substrate, and then the other electrode is laminated with the copper electrode in contact with the conductive particles, and a pressure of 3 MPa is applied thereto to perform pressure bonding to obtain a laminate. body. Thereafter, the laminate is at 180. (: heating is performed for 1 minute, whereby the anisotropic conductive paste is hardened to obtain a bonded structure. I59121.doc -36- 3 201222558 For the obtained joined structure, whether or not cracks are present in the conductive layer of the conductive particles The crack of the conductive layer is determined by the following criteria. [Criteria for the determination of cracks in the conductive layer] 〇: There is no large crack in the conductive layer, and the resin particles are not exposed. △: There is a large crack in the conductive layer, and the resin particles are slightly Exposed to X. There is a large crack in the conductive layer, and the resin particles are exposed to a large extent. (2) Conduction reliability. The relative structure of one of the connected structures obtained by the above-mentioned (i) evaluation by the four-terminal method. The connection resistance between the electrodes was measured, and the conduction between the electrodes was evaluated. The conduction reliability was determined based on the following criteria. [The criterion for determining the conduction reliability] 〇: 100 connection structures were all turned on △ : 100 connected structures were not The number of conduction is 1 or 2 x: The number of non-conducting bodies in 100 connection structures is 3 or more. (3) Vickers hardness is used. "DUH-W201" manufactured by Shimadzu Corporation The Vickers hardness of the copper-tin layer in the obtained conductive particles was measured. The Vickers hardness was determined by the following criteria. [Standard of Vickers hardness] A: Vickers hardness exceeding 500 B: Vickers hardness was 1〇〇 Above, below 500, C: Vickers hardness is less than 1 〇〇 (4) Melting point: 0.2 to 0.5 mg of conductive particles are placed in an aluminum pan, and "DSC2920" manufactured by TA Instruments 159121.doc -37-201222558 is used for heating rate. The Heat-Flow Curve was obtained by scanning under the condition of lOt/min. The temperature value indicated by the peak of the melting peak visible on the curve was analyzed as the melting (5) metal content. In a glass-made conical flask, conductive particles 〇 5 g and aqua regia (35 〇 / 〇

The hydrochloric acid solution is 15 mL, 70 ° /. Mix 5 mL of nitric acid in 20 mL, warm in a warm water bath at 70 ° C and place for 5 minutes. After the flask was taken out from the water bath, it was naturally cooled so that the liquid temperature in the flask became 40 ° C or less. After cooling, an acidic solution containing metal ions and resin particles was filtered using a glass funnel and filter paper (filter paper manufactured by Advantec, N. 5C). The solid-liquid separation was carried out, and an acidic solution containing metal ions was taken out for 1 〇〇, and then 1 mL was dispensed in a minute amount of a liquid tube, and diluted 1 time with pure water to obtain a diluted solution. The dilution obtained by the ritual is measured by ICP (Inductively Coupled Plasma, ULTIMA2 manufactured by Horiba, Ltd.), and the weight of the metal of the conductive layer and the amount of each metal are calculated based on the obtained metal ion thick shoulder. The result is not less than the following 矣彳 φ in "1 garment 1τ in Table 1 below, "_" means unspoken i| price 0 159121.doc

• 38· 201222558 [1<] Example 11 <Electroless plating 〇§ 0 0 < 〇ν〇Example 10 Cup electroless plating 〇S 〇0 < ο m so Example 9 < Plating 〇S 0 〇<S Ό 1 Example 8 <Electroless plating 〇〇〇< 〇Example 7 CQ m Electroless plating 〇§ 0 0 < o fO so i Example 14 < · 碡 electroless plating 〇 <<1 CQ » 〇 ON Example 6 CQ electroless plating _1 〇〇〇 < o SO Comparative Example 4 < 1 Electroless plating S3 XXUS • ο Example 5 disc electroless plating 〇S 0 〇< o ro so Comparative Example 3 < 碡^ Electroless plating g XX CQ »〇Example 4 < m Electroless plating 〇S 0 〇< o Comparative example 2 < Electroless plating 〇SXX 1 1 Example 3 <Male electroless plating S 〇0 〇< Comparative Example 1 < Electroless plating only copper layer 〇SXX 1 1 Example 2 < Electrolytic plating 〇〇 < O 卜 Example 13 < Physical/mechanical method 〇S 0 0 < ο cn VO Example 1 <Electroless plating 〇S 〇〇< ο 实施 Example 12 <Physical/mechanical method 〇S 〇0 < 630 Resin particles Types of protrusions, presence or absence of insulating particles, presence or absence of second conductive layer, formation of first conductive layer, presence or absence of alloying copper content (% by weight), tin content (% by weight), conductive layer cracking reliability, Vickers hardness, melting point resin particles Types of protrusions, presence or absence of insulating particles, presence or absence of second conductive layer, formation of first conductive layer, presence or absence of alloying copper content (weight tin content (% by weight), conductive layer cracking reliability, Vickers hardness melting point -39- 159121 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention. Fig. 2 is a plan view showing a conductive particle according to a second embodiment of the present invention. Fig. 3 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention. Fig. 4 is a cross-sectional view for explaining a method of obtaining the electroconductive particles shown in Fig. 1. Fig. 5 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention. Fig. 6 is a cross-sectional view showing a conductive particle according to a fourth embodiment of the present invention. [Description of main components] 1. Conductive particles 2 Substrate particles 2a Surface 3 Copper-tin layer 3a Surface 11 Conductive particles 11a Surface 12 Copper - Tin layer 12a surface 13 core material • 40 · 159l21.doc

201222558 14 Projection 15 Insulating particle 21 Connection structure 22 First connection target member 22a Upper surface 22b Electrode 23 Second connection target member 23a Lower surface 23b Electrode 24 Connection portion 51 Conductive particles 52 Copper layer 52a Surface 53 Tin layer 61 Conductive Particles 62 Second Conductive Layer 71 Conductive Particles 72 Copper-tin Layer 159121.doc -41 -

Claims (1)

201222558 VII. Patent Application Range: 1. A conductive particle comprising a substrate particle and a copper-tin layer containing copper and tin disposed on a surface of the substrate particle, wherein the steel-tin layer contains copper and The alloy of tin, the content of the above copper in the entire copper/tin layer is more than 20% by weight. /. And it is 75 weight. /❶ below, and the content of tin is 25% by weight or more and less than 8 % by weight. 2. The conductive particles according to claim 1, wherein the copper-tin layer has a melting point of 550 ° C or higher. 3. The conductive particles of claim 1 or 2, wherein the copper content of the copper-tin layer as a whole is 40% by weight. /◦ or more, 6〇% by weight or less, and the content of tin is 40% by weight or more and 6% by weight or less. 4. The electroconductive particle of claim 1 or 2, which has a protrusion on the surface. 5. The electroconductive particle of the item 丨 or 2, which has an insulating material disposed on the surface of the copper-tin layer. 6. The object of claim 5, wherein the insulating material is an insulating particle. An anisotropic conductive material containing the conductive particles according to any one of the claims and the binder resin. 8. A connection structure that includes a first connection target member, a second connection target member, and a connection portion that connects the first and second connection target members, and the connection portion is as claimed in claims i to 6 The conductive particles of any one of them are formed by an anisotropic conductive material containing the conductive particles and a binder resin. 159121.doc