TW200939583A - Circuit connecting material and connecting structure for circuit member - Google Patents

Abstract

Disclosed is a circuit connecting material for electrically connecting two circuit members each with a circuit electrode formed thereon in such a state that the circuit electrodes are disposed to face each other. The circuit connecting material contains an adhesive agent composition and electroconductive particles. The electroconductive particle comprises a nucleus formed of an organic polymer compound and a metal layer covering the nucleus. The metal layer has protrusions protruded toward the outside of the electroconductive particle. The metal layer is formed of nickel or a nickel alloy. Upon the application of a pressure to the electroconductive particle, the metal layer located on the inner part of the protrusion sinks in the nucleus.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a connection structure of a circuit connecting material and a circuit member. [Prior Art] Connection of a liquid crystal display and a transfer tape package (hereinafter referred to as "TCP"), connection of a flexible circuit board (hereinafter referred to as "FPC") and TCP, or FPC and printed circuit The connection between the circuit members of the board connection is a circuit connecting material (for example, an isotropic conductive adhesive) in which conductive particles are dispersed in an adhesive. Further, recently, in a state in which a semiconductor germanium wafer is mounted on a substrate, a so-called flip chip in which a semiconductor germanium wafer is face-down and directly mounted on a substrate is connected without connecting wire-bonding between circuit members. Construction. Even in the flip chip mounting, a circuit connecting material such as an anisotropic conductive adhesive is used for the connection between the circuit members (refer to Patent Documents 1 to 5). [Patent Document 1: JP-A-59-120436] Patent Document 2: JP-A-60-1-91228 Patent Document 3: Japanese Patent Laid-Open No. Hei 1-251787 Patent Document 4: Japanese Patent Application No. JP-A-2001-189171, JP-A-2001-189171, JP-A-2005-166438, JP-A-2009 In recent years, as the size and thickness of electronic devices have increased, the density of circuits formed in circuit components has increased. The distance between adjacent electrodes and the tendency of the electrode width to be very narrow have occurred. The formation of the circuit electrode is carried out by forming a metal which is a circuit base on the entire surface of the substrate, coating and hardening the resist at a portion where the circuit electrode should be formed, and etching the portion other than the acid or alkali. However, in the state of the high-density circuit, when the metal unevenness formed on the entire surface of the substrate is increased, the etching time is different between the concave portion and the convex portion. Therefore, precise etching cannot be performed, and there is a so-called adjacent circuit. A problem occurs when a short circuit or a wire break occurs. Therefore, it is required that the surface of the electrode of the high-density circuit has small unevenness, that is, the surface of the electrode is flat. However, in the state in which the above-mentioned conventional circuit connecting material is used to connect between the opposing flat electrode electrodes, the adhesive resin remains between the conductive particles included in the circuit connecting material and the flat electrode. The problem of sufficient electrical connection and long-term reliability between the opposing circuit electrodes cannot be ensured. Therefore, in order to solve such a problem, it is proposed to use a circuit connecting material having a plurality of protrusions on the surface side and containing the outermost layer of the metal layer as gold (Au) conductive particles for use between the opposing circuit electrodes. Connection (refer to Patent Document 6). The circuit connection structure using the circuit connection material can be connected to -6-200939583 to ensure sufficient electrical connection and long-term reliability between the opposing circuit electrodes, which requires a better electrical connection between the opposing circuit electrodes. The sexual connection also increases the long-term reliability of the electrical characteristics between the circuit electrodes. The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a circuit connecting material capable of achieving a good electrical connection between opposing circuit electrodes while sufficiently improving long-term reliability of electrical characteristics between circuit electrodes. The connection structure of the circuit member using the circuit connection material, and the connection method of the electric Φ path member. [Means for Solving the Problem] The outermost layer of the metal layer constituting the conductive particles, which is used for a conventional circuit connecting material and having protrusions on the surface, is made of Au. Au is a relatively soft metal. Therefore, when pressure is applied during circuit connection, the protrusions are deformed, and long-term continuity with respect to the circuit electrodes is not easily obtained. Then, the inventors of the present invention thoroughly studied the results of the whole process, and as a result, it was considered that the material of the metal layer constituting the conductive particles (the outermost layer in the state in which the metal layer is a plurality of layers) was changed to be harder than Au. Metal. Then, the inventors found that the electrical connection between the opposing circuit electrodes affects the hardness of the metal layer of the conductive particles and the reaction force of the plastic from the core body composed of the organic polymer compound. A metal layer which occurs in the inner portion of the protrusion at the time of circuit connection is embedded in the core body. That is, in the connection of the circuit member using the circuit connecting material of the present invention, the protrusion of the surface of the conductive particle is embedded on the side of the circuit electrode by the pressure at the time of circuit connection, and at the same time, the metal layer of the inner portion of the protrusion is It is also embedded in the body side of the core 200939583, and the protrusion is pushed to the circuit electrode side by the reaction force of the plastic to form a circuit connection portion which is also embedded in the circuit electrode. As a result, the circuit connecting material of the present invention can find a good connection between the opposing circuit electrodes and improve the long-term reliability of the electrical characteristics between the circuit electrodes. The invention provides a circuit connecting material, which is a circuit connecting material used for forming two circuit members of a circuit electrode to electrically connect the circuit electrodes, and the circuit connecting material comprises an adhesive composition and conductive particles. 'The conductive particles are made of a core body made of an organic polymer compound and a metal layer covering the core body. The metal layer has a protrusion protruding toward the outside of the conductive particles. The metal layer is made of nickel or a nickel alloy, and the conductive particles are pressurized. At the time, the metal layer of the inner portion of the protrusion is embedded in the core body. The present invention also provides a circuit connecting material, which is a circuit connecting material used for forming two circuit members of a circuit electrode to electrically connect the circuit electrodes, and the circuit connecting material contains an adhesive composition and is electrically conductive. The particle 'conductive particle includes a core body formed of an organic polymer compound and a plurality of metal layers covering the core body, and the metal layer has a protrusion protruding toward the outside of the conductive particle. The outermost layer of the metal layer is made of nickel or a nickel alloy. When the conductive particles are applied with pressure, the metal layer of the inner portion of the protrusion is embedded in the core body. Such a circuit connecting material is capable of achieving a good electrical connection between the opposing circuit electrodes while sufficiently improving the long-term reliability of the electrical characteristics between the circuit electrodes. In the circuit connecting material of the present invention, the Vickers hardness of the outermost layer of the metal layer or the metal layer is preferably 400 to 1000 200939583. Thereby, the opposing circuit electrodes can be made good, and the circuit polarity can be further improved. In addition, the present invention provides a circuit for forming a circuit electrode, wherein the circuit electrode is disposed between the circuit member and the circuit connecting member that is heated and pressurized, and the hardened material of the circuit connecting member is contained in the circuit connecting material. In the inner part, the metal layer is embedded in the core body. Since the connection structure of the circuit member is used, it is possible to obtain a circuit state between the circuit electrodes, and the electrical state of the circuit through which the conductive particles are opposed can be maintained by the circuit connection material, thereby sufficiently improving the electrical characteristics. The connection structure of the circuit member, at least one of the surface of the dipole is preferably referred to as "ITO" or indium-zinc oxide (right-formed. Like this, by the surface of the circuit electrode. In addition to the electrodes of the Au, Ag, Sn, and Pt groups, there is also a so-called base metal prevention. In addition, the present invention provides a circuit as a circuit electrode, which is arranged such that the circuit electrodes are paired with the aforementioned circuit connection material and are heated. The inner portion of the protruding portion of the conductive particle: the connection structure of the long-term reliable member in which the electrical connection between the conductive particles is further changed, and the two circuit members are opposed to each other, and then the circuit electrode is electrically connected to the present invention. The circuit connecting material has a good electrical connection between the protruding portions of the conductive particles and the above-mentioned circuit connecting material. The good electrical connection between the electrodes is hardened for a long time. In the long-term reliability of the circuit, the electric circuit of the two circuit components - tin oxide (hereinafter, referred to as "IZO" below), the surface of the metal consisting of ITO or IZO, the advantages of oxidation of A1 or Cr The connecting method of the member is pressed between the two circuit members in the shape direction until the metal layer of the circuit connecting material is embedded in the core body, and the circuit electrodes are electrically connected by -9-200939583. The long-term reliability of the electrical characteristics is a sufficiently good connection structure of the circuit components. [Effect of the Invention] If the material is connected by the circuit of the present invention, a good electrical connection between the opposing circuit electrodes can be achieved. At the same time, the long-term reliability of the electrical characteristics between the circuit electrodes is sufficiently improved. Further, according to the present invention, it is possible to provide a connection structure of the circuit member which is sufficiently good in long-term reliability of electrical characteristics between the circuit electrodes and the connection thereof. [Embodiment] [Best Embodiment of the Invention] In the following, the present invention is referred to as needed, and the ideal embodiment of the present invention is In the drawings, the same elements are denoted by the same reference numerals, and the description thereof will not be repeated. The positional relationship between the upper and lower sides and the like is not particularly limited. In addition, the dimensional ratio of the drawings is not limited to the illustrated ratio. [Connection Structure of Circuit Member] - Fig. 1 is a schematic cross-sectional view showing an example of a connection structure of a circuit member of the present invention. The connection structure 1 of the member is provided with the first circuit member 30 and the second circuit member 40' that face each other between the first circuit member 30 and the second circuit member 40, and the circuit connection member 1 is connected. The circuit connecting member 1 is obtained by hardening a circuit connecting material including an adhesive composition and conductive particles 12 having a plurality of protrusions 14 on the surface of Table-10-200939583. Therefore, the circuit connecting member 1 contains the insulating material 11 and the conductive particles 12. Here, the insulating material 11 is composed of a cured product of the adhesive composition. The first circuit member 30 includes a circuit board (first circuit board) 31 and a circuit electrode (first circuit electrode) 32 formed on the main surface 31a of the circuit board 31. The second circuit member 40 includes a circuit board 41 and a circuit electrode (second circuit electrode) 42 formed on the principal surface 41a of the circuit board 41. The surface of the circuit electrodes 32, 42 of the circuit boards 31, 41' is flat. Further, in the present invention, the term "the surface of the circuit electrode is flat" means that the surface unevenness of the circuit electrode is 2 Onm or less. The thickness of the circuit electrodes 32, 42 is preferably 50 nm or more. In a state where the thickness of the circuit electrodes 32, 42 is less than 5 Onm, the protrusion portion 14 on the surface side of the conductive particle 12 located in the circuit connecting material can be brought into contact with the circuit electrodes 32, 42 while being pressed. Go to the circuit boards 31, 41. In this state, there is a tendency that the contact resistance of the circuit electrodes 32, 42 and the conductive particles 12 is reduced and the connection resistance is increased. Further, in terms of manufacturing cost and the like, the thickness of the circuit electrodes 32 and 42 is preferably 100 nm or less, more preferably 500 nm or less. The material of the circuit electrodes 32 and 42 is a metal of Au, Ag, Sn, or Pt, or 11'0, 120, 八1, (1:1). Especially, the material of the circuit electrodes 32 and 42 is ITO or IZO. In the state of the present invention, the electrical connection system is remarkably good, and the effects of the present invention are exhibited. Further, the circuit electrodes 32 and 42 can be configured as the whole by the above-mentioned substances. The surface of the circuit board 3 1 and 41 is not particularly limited, but is usually an organic insulating material, glass or tantalum. Specific examples of the first circuit member 30 and the second circuit member 40 A series of substrates such as semiconductor wafers, resistor chips, and capacitor wafers, and printed circuit boards are provided. In these circuit members 30 and 40, circuit electrodes (circuit terminals which can be singular due to different states) are usually provided. In addition, the form of the connection structure of the circuit member includes the connection structure of the 1C wafer and the wafer mounting substrate, and the connection structure between the electric circuits. The first circuit member 30 is provided with an insulating layer between the first circuit electrode 32 and the circuit board 31, and may be provided between the second circuit electrode 42 and the circuit board 41 in the second circuit member 40'. The insulating layer is not particularly limited as long as it is composed of an insulating material, but 'generally consists of an organic insulating material, bismuth oxide or tantalum nitride. Next, the connection of the circuit member In the structure 1, the opposite circuit electrode - 32 and the circuit electrode 42 are electrically connected through the conductive particles 12. That is, the conductive particles 12 are directly in contact with both of the circuit electrodes 32, 42. Specifically, The protrusions (also referred to as "protrusions") 14 of the conductive particles 12 penetrate the insulating material 11 and contact the first circuit electrode 32 and the second circuit electrode 42. Therefore, the connection between the circuit electrodes 32 and 42 can be sufficiently reduced. Electricity-12- 200939583 Because the smoothest 4 2 electric electricity is electrically connected to the 12-resistance, it can make a good electrical connection between the circuit electrodes 3 2 and 42. This can make the circuit electrodes 3 2, 42 Current between The flow becomes smooth, and the function of the circuit can be sufficiently exerted. One of the plurality of protrusions 14 of the conductive particles 12 is embedded in the circuit electrode 32 or the circuit electrode 42. In this state, it is increased more. The contact area between the protrusions 14 of the conductive particles 12 and the circuit electrode 32 further reduces the connection resistance. 0 In the connection structure 1 of the circuit member, it is preferable that the first circuit electrode 32 has a surface area of at least one side of the second circuit electrode 42. 5,000 μm 2 or less, and the number of average guided particles between the first circuit electrode 32 and the second circuit electrode 42 is one or more. Here, the average number of conductive particles means the average 値 of the number of conductive particles per circuit electrode. In this state, the connection resistance between the opposing circuit electrodes 3, 42 can be sufficiently reduced. Further, in a state where the average number of conductive particles is three or more, a more excellent connection resistance can be achieved. This is because the connection resistance between the opposing 电路 circuit electrodes 32, 42 is sufficiently reduced. Further, in the state where the average number of conductive particles between the circuit electrodes 32 and 42 is one or less, the - connection resistance is excessively high, and the electronic circuit cannot be normally started. Hereinafter, the circuit connecting member 1 will be described in detail. The road connecting member 1 is formed into a film shape, and as described above, it is obtained by performing a hardening treatment on a circuit connecting material containing the conductive particles 1 2 having the protrusions 14 on the surface side and the adhesive composition. The circuit connecting member 1 is made of an insulating material 11 and conductive particles. The conductive particles 12 are described later in detail, but as shown in Figs. 13-32 200939583 (a) and (b), a plurality of protrusions 14 are provided on the surface side thereof. Next, in the connection structure 1 of the circuit member, the opposing circuit electrode 32 and the circuit electrode 42 are electrically connected to each other through the conductive particles 12. That is, the conductive particles 12 are in direct contact with both of the circuit electrodes 32, 42. Specifically, the protruding portion 14 of the conductive particles 12 penetrates the insulating material 11 and contacts the first circuit electrode 32 and the second circuit electrode 42. Further, the metal layer 22 of the inner portion of the protruding portion 14 of the conductive particle 12 is embedded on the side of the core body 21a, and at this time, the protruding portion 14 is pressed up to the circuit electrodes 32, 42 by the reaction force of the plastic of the core body 21a. On the side, the projection 14 is more embedded in the circuit electrode. Therefore, the contact area between the conductive particles 12 and the circuit electrodes 32, 42 can be increased, the connection resistance between the circuit electrodes 32, 42 can be sufficiently reduced, and a good electrical connection between the circuit electrodes 32, 42 can be performed. Therefore, the flow of current between the circuit electrodes 32 and 42 can be made smooth, and the function of the circuit can be sufficiently exhibited. [Circuit Connection Material] (Conductive Particles) The conductive particles 1 2 are composed of conductive particles (bulk portion) and a plurality of protrusions 14 formed on the surface of the particles. Here, the plurality of protrusions 14 are made of a metal having conductivity. Fig. 2 is a cross-sectional view showing various forms of conductive particles contained in the circuit connecting material of the present invention. The conductive particles 12 shown in Fig. 2(a) are composed of a core body 21 composed of an organic polymer compound and a metal layer 22 formed on the surface of the core body 21. The core body 21 is composed of a core portion 21a and a protrusion portion 21b formed on the surface of the core portion 21a. The metal layer 22 is on the surface side thereof and has a plurality of protrusions 14. The metal layer 22 covers the core body 21, and protrudes toward the outer side of the conductive particles at a position corresponding to the protrusions 2 1 b , and a portion of the protrusions is a protrusion portion 14. The core body 21 is lower in cost than the core body composed of metal, and Q, and the elastic deformation range is widened with respect to the dimensional change at the time of thermal expansion or press-bonding, and therefore, is more suitable as a circuit connecting material. . Examples of the organic polymer compound constituting the core portion 21a in the core body 21 include, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyalkylene resin, a polybutadiene resin, or a copolymer of these. You can use cross-linking these people. The average particle diameter of the core portion 21a in the core body 21 is preferably 1 to 4 μm, more preferably 2 to 4 μm, even more preferably 2.5 to 3. 5 μm. When the average particle diameter is less than ιμιη, there is a tendency that secondary aggregation of particles occurs and insulation between adjacent circuits is insufficient. On the other hand, when the average particle diameter exceeds 4 μm, the area of the adhesive composition is removed at the time of circuit connection, and thus the tendency of the adhesive composition to be insufficiently removed occurs. Further, the average particle diameter of the core body 21 of the present specification means the average particle diameter of the core portion 21a, and can be measured by observing the cross section of the conductive particles by using a particle size distribution measuring apparatus or an electron microscope. Examples of the organic polymer compound constituting the protrusion 21b of the core body 21 include, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a poly-15-200939583 decane resin, a polybutadiene resin, or the like. Copolymers can be used to crosslink these. The organic polymer compound constituting the protrusion portion 21b may be the same as the organic polymer compound constituting the core portion 21a, or may be different from the organic polymer compound constituting the core portion 21a. Further, the average particle diameter of the projections 21b is preferably 50 to 500 nm. The core body 21 can be formed by adsorbing a plurality of protrusions 21b having a diameter smaller than the diameter of the core portion 21a on the surface of the core portion 21a. The method of adsorbing the protrusion 21b on the surface of the core portion 21a is, for example, a surface treatment of particles of both or one side with a dilute solution of various coupling agents such as decane, aluminum, titanium, or the like, and mixing two The method of attachment. As the material of the metal layer 22, Cu, Ni or a Ni alloy, Ag or Ag alloy is preferable, and Ni or a Ni alloy is preferable. Further, in a state in which the metal layer 22 is composed of a plurality of metal layers, the material of the outermost layer of the metal layer 22 is preferably Ni or a Ni alloy. Examples of the Ni alloy series include Ni-B, Ni-W, Ni_B, Ni-W-Co, Ni-Fe, and Ni-Cr. The hardness of the metal layer 22 is preferably a Vickers hardness of 400 to 1,000, more preferably 500 to 800. Further, in a state where the metal layer 22 is composed of a plurality of metal layers, the Vickers hardness of the outermost layer of the metal layer 22 is preferably from 400 to 1,000, more preferably from 50,000 to 800. When the Vickers hardness of the metal layer is less than 400, the metal layer of the protrusion is deformed at the contact of the electrode of the circuit, and the embedding of the circuit electrode is weakened, and the contact area is reduced to increase the connection resistance. In addition, when the Vickers hardness of the metal layer exceeds 1 ,, the metal layer is broken due to the deformation of the particles when the connection is made to 200939583, and the tendency to increase the connection resistance is caused by the state in which the conduction path between the electrodes of the circuit is blocked. . The metal layer 22 can be formed by plating these metals with the electroless plating method for the core body 21. The electroless plating method is roughly classified into a discontinuous mode and a continuous dropping method, but the metal layer 22 can be formed even by any of the methods. The thickness (plating thickness) of the metal layer 22 is preferably 65 to 125 nm φ , more preferably 75 to 100 nm, and even more preferably 80 to 90 nm. The connection resistance between the circuit electrodes 32 and 42 can be made better by the thickness of the metal layer 22 being such a range. Here, the thickness of the metal layer 22 of the conductive particles in the present specification means the thickness of the metal layer portion not including the protrusion portion 14, and can be measured by an electron microscope. When the thickness of the metal layer 22 is less than 65 nm and the thickness of the shovel is thin, the connection resistance tends to increase. When the thickness exceeds 125 nm, aggregation occurs between the conductive particles during plating, and it is easy to be adjacent to the circuit. A tendency to generate a short circuit between the electrodes Q occurs. Further, in the conductive particles 12, the mixing ratio of the particles of the metal layer - 22 completely removed by the core body 21 is preferably 25% of the particles and less than 5%, more preferably 1.0% or even more preferably. It is less than 0.1%. The mixing ratio of the particles of the metal layer 22 can be completely peeled off by the core body 21, and the range between the circuit electrodes 32 and 42 can be surely turned on. In the case where the particles of the metal layer 22 are completely peeled off by the core body 21, the mixing ratio is 5% or more, and there is a tendency that the connection resistance becomes large because the particles which are not electrically conductive are present on the electrode. -17- 200939583 The conductive particles 12 of the present invention also have a state in which the core body 21 is partially exposed. In view of the connection reliability, the coverage of the surface area of the metal layer 22 with respect to the core body 21 is preferably 70% or more, more preferably 80 to 100%. The coverage of the metal layer 22 can be made into such a range, and the connection resistance between the circuit electrodes 32, 42 is made better. When the coverage of the metal layer 22 is less than 70%, the conduction area of the surface of the conductive particles is small, and thus the connection resistance tends to increase. The height of the protrusions 14 of the conductive particles 12 is preferably 65 to 500 nm q , more preferably 100 to 300 nm. Further, the distance S between the adjacent projections 14 is preferably 100 nm or less, more preferably 500 nm or less. Further, the distance S between the adjacent protrusions 14 is such that the adhesive composition does not enter between the conductive particles 12 and the circuit electrodes 32, 42. Therefore, in order to sufficiently contact the conductive particles 12 and the circuit electrodes 32, 42, it is preferable that at least 5 Onm or more. Further, the height Η of the protrusions 14 of the conductive particles 12 and the distance S between the adjacent protrusions 14 can be measured by an electron microscope. Further, as shown in Fig. 2(b), the conductive particles 1 2 can constitute the core body 21 only by the core portion 21a. In other words, in the conductive particles 12 shown in Fig. 2(a), the protruding portion 21b may not be provided. The conductive particles 12 shown in Fig. 2(b) can be obtained by forming the metal layer 22 on the surface of the core body 21a by plating the surface of the core body 21a with metal. Here, a description will be given of a plating method for forming the bumps 14. For example, the protrusions 14 can be formed by adding a plating solution having a concentration higher than that of the first plating solution in the middle of the electric shovel reaction so that the concentration of the plating solution becomes neither -18-200939583. In addition, the pH of the plating solution can be adjusted, for example, by the pH of the nickel plating solution to become 6, thereby obtaining a blister-like metal layer, that is, a metal layer 22 having protrusions 14 (Moon Moon, Surface Technology, Vol .48, No. 4, pp. 429-432, 1997). Further, as a stabilizing agent which contributes to the stability of the plating bath, a smooth metal layer (film) is formed in the state in which glycine is used, and relatively, in the state in which tartaric acid or DL-malic acid is used, blister can be obtained. The tumor-like membrane 'is the metal layer 22 with φ protrusions 14 (荻原, amorphous plating, Vol.36, pp. 3 5~3 7 pages, 1 994; 荻原, Circuit Construction Society, Vol .10, Νο·3, 148~152, 1 995). The metal layer 22 may be composed of a single metal layer or a plurality of metal layers. (Adhesive Composition) The adhesive composition is preferably (1) a composition containing a latent hardener of an epoxy resin and a cyclic oxime resin, (2) a radical polymerizable substance, and a heat generation. A composition of a free radical hardener, or a mixed composition of (1) and (2). First, (1) a composition containing a latent hardener of an epoxy resin and an epoxy resin will be described. As the foregoing epoxy resin series, bisphenol quinone type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol aldehyde type epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, alicyclic epoxy resin, epoxy propyl ester epoxy resin, epoxy propyl amine epoxy resin, Bene-19- 200939583 醯A urea type epoxy resin, an isocyanate type epoxy resin, or an aliphatic chain type epoxy resin. These epoxy resins can be halogenated or hydrogenated. These epoxy resins can be used in two or more types. The epoxy resin can be hardened as a latent hardener. Examples of such a latent curing agent include an anionic polymerizable catalyst type hardener, a cationic polymerizable catalyst type hardener, and a polyaddition type hardener. These systems may be used singly or as a mixture of two or more kinds. Among these, an anionic or cationically polymerizable catalyst type hardener is preferred because of its good rate of hardenability and the need to consider chemical equivalents. Examples of the anionic or cationic polymerizable catalyst type hardeners are imidazole, anthraquinone, boron trifluoride-amine complex, phosphonium salt, amine imide, diamine maleonitrile, melamine and Its derivatives, polyamine salts, dicyandiamide; these denatures can also be used. Examples of the polyaddition type hardener include polyamines, polythiols, polyphenols, and acid anhydrides. In the state in which a tertiary amine or an imidazole is used as an anionic polymerizable catalyst hardener, the epoxy resin is at a temperature of from 160 ° C to 200 ° C, by a number of 10 seconds to several Hardening is performed by heating in an hour. Therefore, the usable time (applicable period) is relatively long, and therefore, it becomes desirable. The cationically polymerizable hardener is preferably a photosensitive gun salt which hardens an epoxy resin by an energy ray (mainly an aromatic diazonium salt or an aromatic sulfonium salt). Further, as the epoxy resin which is hardened and activated by heating in addition to the irradiation of energy rays, an aliphatic sulfonium salt is used. Such a hardener is characterized by so-called quick-curing property, and therefore it is desirable. -20- 200939583 Microcapsules are coated with these latent curing agents by high molecular weight materials such as polyurethanes, polyesters, metal films such as nickel and copper, and inorganic materials such as calcium silicate. It is possible to extend the usable time and, therefore, it becomes ideal. Next, the description will be made on (2) a composition containing a radical polymerizable substance and a curing agent which generates free radicals by heating. The radically polymerizable substance is a substance having a φ energy group which is polymerized by a radical. Examples of such a radically polymerizable material include a compound of acrylate (including the corresponding methacrylate, which is the same below), and propylene oxidation (including the corresponding methacrylic oxidation. The same applies hereinafter) of the compound and maleic anhydride. An imine compound, a cis-methylbutenediamine resin, or a phenolphthalein imide resin. The radically polymerizable substance can be used in the form of a monomer or an oligomer, and a monomer and an oligomer can also be used. Specific examples of the acrylate compound include methacrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, decylene glycol diacrylate, diethylene glycol diacrylate, and trishydroxyl Methylpropane triacrylate, tetramethylol methane tetraacrylate, 2-hydroxy-1,3-dipropene oxide propane, 2,2-bis[4-(propylene oxymethoxy)phenyl]propane _, 2,2-bis[4-(propylene oxide polyethoxy)phenyl]propane, dicyclopentenyl acrylate, tricyclodecenyl acrylate, tris(propylene oxime oxirane) isocyanate, amine Ethyl methacrylate acrylate. These systems may be used alone or in combination of two or more. Further, a polymerization inhibiting agent such as hydroquinone or methyl ether hydroquinone may be used as needed. Further, from the viewpoint of improving heat resistance - 21 to 200939583, the acrylate compound is preferably at least one selected from the group consisting of a dicyclopentenyl group, a tricyclodecenyl group, and a triazine ring. Substituent. The above-described maleic anhydride imide compound contains at least two or more maleic anhydride imide groups in the molecule. Examples of such a maleic anhydride imide compound include, for example, 1-methyl-2,4-dimaleic anhydride imide benzene, hydrazine, Ν'-m-phenylene bismaleimide, hydrazine, and hydrazine. Ν'-ρ-phenylene bismaleimide, N,N'-m-methylphenyl bismaleimide, imine, Ν'-4,4-biphenyl bismaleic anhydride Imine, 1 -4,4-(3,3'-dimethylbiphenyl 0 ) bismaleic acid imide, hydrazine, Ν '-4,4- (3,3'-dimethyl Bis-phenylmethane) bis-maleic anhydride imide, hydrazine, Ν'-4,4-(3,3'-diethyldiphenylmethane) bis-maleic anhydride imine, hydrazine, Ν'- 4,4-diphenylmethane bismaleimide, imine-4,4-diphenylpropane bismaleimide, >1,:^'-3,3'-diphenyl Bismuth maleic anhydride imide, hydrazine, Ν'·4,4-diphenyl ether bis-maleic anhydride imide, 2,2-bis(4-(4·maleic anhydride) Phenyl)propane, 2,2-bis(3-s-butyl-4,8-(4-maleic anhydride acetoxyphenoxy)phenyl)propane, 1,1-bis(4- (4-maleic anhydride imide benzene ◎ oxy) phenyl) decane, 4, 4'-cyclohexylidene-bis (1_ (4-malay) Anhydride acetoxyphenoxy))-2-cyclohexylbenzene, 2,2-bis(4-(4-maleic anhydride)-aminophenoxy)phenyl)hexafluoropropane. These systems may be used singly or in combination of two or more. The cis-methylbutenediamine resin described above is polymerized by cis-methylbutenediamine compound having at least one cis-methylbutenediminoimine group in the molecule. . As a series of cis-methylbutenediamine compounds, for example, phenyl cis-methylbutene diimine, 1-methyl-22- 200939583-based-2,4-di-cis-methylbutene dioxime Iminobenzene, N,N'-m-phenylene bis-methylbutenyl imine, N,N'-p-phenylene bismethylbutenediamine, N,N' _4,4-biphenylene bis-methylbutenylimine, N,N'-4,4-(3,3-dimethylbiphenyl)bis-cis-methylbutenylene Amine, :^,\'- 4.4- (3,3-dimethyldiphenylmethane) bis-cis-methylbutenediamine, N,N'-4,4-(3,3-di Ethyldiphenylmethane) bis-cis-methylbutenediamine, hydrazine, Ν'·4,4·diphenylmethane bis-methylbutenylene diimide, φ 1^['- 4,4-diphenylpropane bis-cis-methylbutenediamine, ^^['-4,4-diphenyl ether bis-cis-methylbutenediamine, hydrazine, hydrazine -4,4-diphenyl-di-bis-methylbutenylimine, 2,2-bis(4-(4-cis-methylbutenylimidophenoxy)phenyl)propane , 2,2-bis(3-8-butyl-3,4-(4-cismethylbutenylenediamine phenoxy)phenyl)propane 1,1-bis(4-(4-cismethylbutenylimidophenoxy)phenyl)decane, 4,4'-cyclohexylidene-bis(1-(4-cis) Methylbutene diimide phenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-cismethylbutenylenediamine benzoquinoneoxy)benzene Base) hexafluoropropane. These systems can be used singly or in combination of two or more. • The above-described indophenol quinone imine resin is composed of a phenolphthalein imine compound having at least one indophenol quinone imine group in a molecule. As a series of indophenol quinone imine compounds, for example, phenyl nonyl quinone imine, 1-methyl-2,4-bisindole quinone imine benzene, N, N'-m-phenyl bisphenol quinone imine , \,\'-?-Benzenebisindole quinone imine, 1^ small '-4,4-biphenyl bisindole quinone imine, N,N'-4,4- ( 3,3- Dimethylbiphenyl)bisindole quinone imine, N,N'-4.4-(3,3-dimethyldiphenylmethane)bisindole quinone imine, N,N'-4,4- -23- 200939583 (3,3-Diethyldiphenylmethyl) bismuth powder, Imine, hydrazine, Ν'-4,4-diphenylmethane bisphenol quinone imine, Ν, Ν'· 4,4-diphenylpropanebiquinol quinone imine, 1^,>1'-4,4-diphenyl ether bis-imide,]^,]^'-4,4-di Phenyl milled bismuth quinone imine, 2,2-bis(4-(4-nonylphenol imidate phenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3, 4-(4-nonylphenol iminophenoxy)phenyl)propane, 1,1·bis(4-(4-indolyl phthalimidophenoxy)phenyl)decane, 4,4′· Cyclohexyl bis(1-(4-nonylphenol iminophenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-nonylphenol quinone imine phenoxy) Phenyl) hexafluoropropyl . These may be used singly or in combination of two or more kinds. Further, it is preferable to use a radical polymerizable substance having a phosphate structure represented by the following chemical formula (I) in the above-mentioned radical polymerizable substance. In this state, the adhesion strength to the surface of the inorganic material such as metal is increased, so that it is suitable for adhesion between circuit electrodes. [Chemistry 1]

9 〇 ch3 , , 11 || | (H〇)^-P—j-〇CH2CH2-〇—C—C=CH2 In the chemical formula, n represents an integer of 1 to 3. The above-mentioned radically polymerizable substance having a phosphate structure is obtained by a reaction of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate. Specific examples of the radical polymerizable substance having a phosphate structure include a mono(2-methylpropene oxime oxyethyl) acidic phosphorus salt and a bis(2-methylpropenyl oxirane) acidic phosphorus salt. These systems can be used singly or in combination of two or more. -24- 200939583 The amount of the radically polymerizable substance having the phosphate structure represented by the above chemical formula (I) is preferably a film forming material which is preferably bonded to a radically polymerizable substance and, if necessary, The total amount is from 0.01 to 50 parts by mass, more preferably from 0.5 to 5 parts by mass, per 100 parts by mass. The above-mentioned radical polymerizable substance may also be used in the allyl propionate. In this state, the amount of the allyl acrylate is preferably 0. 1 to 10 by mass based on 100 parts by mass of the radically polymerizable material and the film forming material which is blended as needed. More preferably, it is 0. 5 to 5 parts by mass. The hardener which generates free radicals by heating is a hardener which generates decomposition by heating to generate free radicals. As such a hardener series, an oxygen compound or an azo compound is used. Such a curing agent is appropriately selected by the intended connection temperature, connection time, pot life, and the like. From the standpoint of high reactivity and improvement in pot life, it is preferable that the organic peroxide having a half-life of 10 hours and a temperature of 40 ° C or more and a half-life of 1 minute is 0 1801 or less, more preferably a half life of 10 The temperature of the hour is 60 ° C or more and the half-life of 1 minute is 17 ° C below the machine peroxide. In the state where the bonding time is 25 seconds or less, in order to obtain a sufficient reaction rate, it is preferable to use a film forming material which is blended with a radical polymerizable substance and if necessary. The total amount is from 2 to 10 parts by mass, and more preferably from 4 to 8 parts by mass, based on 100 parts by mass. In addition, the amount of the curing agent in the state in which the connection time is not limited is preferably 100 parts by mass based on the total of the radically polymerizable material and the film-forming material of the -25-200939583 which is required to be blended as needed. 0.0 5 to 20 parts by mass, more preferably 0.1 to 10 parts by mass. The hardener which generates free radicals by heating more specifically exemplifies a dimercapto peroxide, a peroxydicarbonate, a peroxyester ketal, a dialkyl peroxide, a hydroperoxide , a methyl methacrylate peroxide. Further, from the viewpoint of suppressing corrosion of the circuit electrodes 32 and 42, the hardener is preferably a concentration of chloride ions or organic acids contained in the hardener of 5,000 ppm or less, and more preferably The organic acid produced by the decomposition after heating is reduced. Specific examples of such a curing agent include a peroxyester, a dialkyl peroxide, a hydroperoxide, and a methyl ketone peroxide, and more preferably a highly reactive peroxyester. Further, the aforementioned hardeners can be used in a moderately mixed manner. As a peroxyester series, cumenyl peroxy neodecanoate,

1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxide peroxydecanoate, t-hexyl peroxy neodecanoate, t -butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxide 2-ethylhexanoate, · 2,5·dimethyl-2,5-di(2- Ethylhexyl peroxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butyl Oxidized 2-ethylhexanoate, t-butyl peroxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, t-hexylperoxyisopropyl monocarbonate Ester, t-butyl peroxy-3,5,5-trimethylhexanoate, butyl butyl laurate, 2,5-dimethyl-2,5-di (m-toluene peroxyl) -26- 200939583) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, t- Butyl peroxyacetate. As a dialkyl peroxide series, α, α bis(t-butyl peroxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t -butyl peroxy) hexane, t-butyl cumenyl peroxide. As the hydroperoxide, a series of diisopropylbenzene hydroperoxide H and cumene hydroperoxide are mentioned. As the dimercapto peroxide series, isobutyl peroxide, 2,4-dichlorophenylhydrazine peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, laurel Mercapto peroxide, stearyl peroxide, amber sulfhydryl peroxide, benzoquinone peroxide toluene, benzoquinone peroxide. As a peroxydicarbonate series, bis-η·propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2 -ethoxymethoxy peroxydicarbonate, bis(2-indenylhexyl peroxy)dicarbonate, dimethoxybutyl peroxydicarbonate, di(3-methyl-3-methyl) Oxybutyl peroxide peroxy) dicarbonate. As a series of peroxy ketals, 1,1 - bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(b-hexylperoxy)cyclohexane, 1 , 1-bis(p-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-(dibutylperoxy)cyclododecane, 2,2-bis(t-butylperoxide) Decane. As a series of methyl ketone peroxides, t-butyltrimethylformamido peroxide, bis(t-butyl)dimethylformamido peroxide, t-butyltrivinylcarbenyl Peroxide, bis(t-butyl)divinylcarbamate-27- 200939583 decyl peroxide, tris(t-butyl)vinylformamidinyl peroxide,dibutyltriallylmethylmercaptoalkyl Oxide, bis(t-butyl)diallylmethyl decyl peroxide, tris(t-butyl)allylmethyl decyl peroxide. These hardeners may be used singly or in combination of two or more kinds thereof, or may be used by mixing a decomposition accelerator, an inhibitor, or the like. Further, these hardeners can be coated with a polyurethane-based or polyester-based polymer material to carry out microencapsulation. The microencapsulated hardener is preferably used to extend the usable time. The film forming material can be added and used in combination with the adhesive composition as needed. In the state in which the constituent material of the liquid material is solidified into a film shape, the film forming material is easily handled, and mechanical properties such as not easily broken or cracked or adhered are imparted. The state (normal temperature and normal pressure) can be processed by the film. As a film forming material series, a phenoxy resin, a polyvinyl acetal resin, a polystyrene resin, a polyvinyl butyral resin, a polyester resin, a polyamide resin, a xylene resin, and a polyurethane Ester resin. Even among these, since it is excellent in adhesion, compatibility, heat resistance and mechanical strength, it is preferably a phenoxy resin. The phenoxy resin is a resin obtained by subjecting a bifunctional benzoquinone to an epihalohydrin to a high molecular weight or a polyfunctional epoxy resin and a bifunctional phenol. The phenoxy resin can be reacted, for example, by reacting a bifunctional phenol with a molybdenum at a temperature of 40 to 120 ° C in a non-reactive solvent in the presence of a catalyst such as an alkali metal hydroxide. Alcohol 0.985~ 200939583 1 . 0 1 5 Moore. Further, 'as a phenoxy resin, from the viewpoint of mechanical properties or thermal properties of the resin', it is particularly preferable to make the equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol to an epoxy group/phenolic hydroxyl group. =1/0.9 to 1/1.1 'In the presence of a catalyst such as an alkali metal compound, an organophosphorus compound or a cyclic amine compound, the amide, ether, ketone or lactone having a boiling point of 120 t or more An organic solvent such as an alcohol is heated at 50 to 200 ° C under the conditions of a reaction solid content of @50% by mass or less, and is subjected to a polyaddition reaction. As the above-mentioned bifunctional epoxy resin series, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diepoxypropyl group Ether, methyl substituted biphenyl diglycidyl ether. The bifunctional phenol type has two phenolic hydroxyl groups. Examples of the bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol oxime, methyl substituted bisphenol quinone, dihydroxy biphenyl ester, and methyl substituted bis. Bisphenols such as hydroxybiphenyl esters. The phenoxy resin can be denatured (e.g., epoxy denatured) by a radical polymerizable functional group or other reactive compound. The phenoxy resin may be used singly or in combination of two or more. The adhesive composition may further comprise a polymer or copolymer having at least one of acrylic acid, acrylate, methacrylate and acrylonitrile as a monomer component. Here, since the stress relaxation is good, it is preferred to use a copolymer-based propylene rubber containing a glycidyl acrylate containing a glycidyl ether group or a propyl epoxide-29-200939583 methacrylate. . The weight average molecular weight of these propylene rubbers is preferably from 200,000 or more in terms of improving the cohesive force of the adhesive. The amount of the conductive particles 12 is preferably from 1 to 30 parts by volume based on 1 part by volume of the adhesive composition, and the amount of the conductive particles can be used separately for the purpose of use. The amount of the conductive particles 12 is more preferably 0.1 to 10 parts by volume from the viewpoint of preventing short circuit of the circuit electrode due to the excess conductive particles 12. ❹ It can also be used in circuit connection materials, and also contains rubber particles, chelating agents, softeners, accelerators, aging inhibitors, colorants, flame retardants, thixotropic agents, coupling agents, phenol resins, melamine resins, isocyanates. . The rubber fine particles may have an average particle diameter of less than twice the average particle diameter of the conductive particles 12 to be blended, and have a storage capacity of 1/2 or less of the storage elastic modulus at room temperature of the conductive particles 12 and the adhesive composition. Elasticity rate. In particular, the rubber particles are made of polysiloxane, acryl latex, SBR, NBR, and polybutadiene rubber. The particles are suitable for use alone or in combination with two types of D. These rubber particles of the three-dimensional cross-linking are excellent in solvent resistance and are easily dispersed in the adhesive composition. In the state in which the circuit connecting material contains the chelating agent, the reliability of the connection and the like are improved, and therefore, it is desirable. The chelating agent can be used if its maximum diameter is 1/2 or less of the particle diameter of the conductive particles 12. If the maximum diameter is 1 /2 or less of the particle diameter of the conductive particles 12, it can be used. In addition, in the case where the particles having no conductivity are used in combination, 'if the agent is less than the diameter of the particles having no conductivity', then the use amount of the -30-200939583 塡-filler is preferably used as opposed to The adhesive composition was made up to 5 to 60 parts by volume in 100 parts by volume. When the amount of the mixture is more than 60 parts by volume, the effect of improving the connection reliability tends to be saturated, and in the case of less than 5 t by volume, there is a tendency that the effect of the addition of the sputum agent is insufficient. The above-mentioned coupling agent contains a compound of a vinyl group, a propylene group, an epoxy group or an isocyanate group to improve the adhesion, and therefore it is preferable. 〔 [Connection method of circuit member] Next, a description will be given of a method of manufacturing the connection structure of the above-described circuit member. First, the first circuit member 30 having the first circuit electrode 32, the second circuit member 40 having the second circuit electrode 42, and the circuit connecting material are prepared. As the circuit connecting material, for example, a circuit connecting material (hereinafter referred to as a film-like circuit connecting material) 50 formed into a film shape is prepared. Fig. 3 is a cross-sectional view showing an embodiment of a film-like circuit connecting material of the present invention. The film-like circuit connecting material 50 is formed into a film-like material by the above-mentioned circuit connecting material ''. The circuit connecting material usually contains the conductive particles 12 having the protrusions 14 on the surface side and the adhesive composition 51. The adhesive composition generally included in the circuit connecting material has adhesiveness and is cured by hardening treatment of the first and second circuit members 3A and 40. The thickness of the film-like circuit connecting material 5 is preferably 1 〇 5 5 μm. Next, the film-like circuit connecting material 50 is mounted on the first circuit member 30. Next, the second circuit member 40 is mounted on the film-like circuit connecting material -31 - 200939583 so that the first circuit electrode 32 and the second circuit electrode 42 face each other. Thereby, the film-like circuit connecting material 50 can be interposed between the first circuit member 30 and the second circuit member 40. At this time, the film-like circuit connecting material 50 is formed into a film shape and is easy to handle. Therefore, when the film-like circuit connecting material 50 is connected, the first circuit member 30 and the second circuit member 40 can be easily interposed between the first circuit member 30 and the second circuit member 40. 2 The connection work of the circuit member 40. Then, the film-like circuit connecting material 50 is heated and pressurized by the first circuit member 30 and the second circuit member 40, and is subjected to a curing process to form a circuit connecting member 1 between the first and second circuit members 30 and 40. . The hardening treatment can be carried out by a general method in which the method is appropriately selected due to the adhesive composition. At this time, the protruding portion 14 of the conductive particles 12 in the circuit connecting member 10 penetrates the insulating material 11 to contact the first circuit electrode 3 2 and the second circuit electrode 42. Further, the metal layer 22 inside the protruding portion 14 of the conductive particles 12 is fitted to the side of the core body 21. At this time, the projections 14 are pressed up to the side of the circuit electrodes 32 and 42 by the reaction force of the plastic (organic polymer) of the core body 21, so that the projections 14 are more closely fitted to the circuit electrodes. Further, in the state where the metal layer or the outermost layer of the conductive particles 12 in the circuit connecting material is Ni or a Ni alloy, it is harder than Au, and therefore, the first or second circuit electrodes 32 and 42 are the most conventional ones. The outer layer is Au conductive particles, and further penetrates into the protrusions 14 to increase the contact area between the conductive particles 12 and the circuit electrodes 32 and 42, thereby stabilizing the connection resistance. Further, 'the Vickers hardness of the metal layer of the conductive particles 12 or the outermost layer thereof is in the range of 400 to 1000, so that the biting of the circuit electrode 32' 42 for the protrusion 14 is changed. Big. Next, by hardening the circuit connecting material, the adhesive composition 51 is hardened, and the adhesion strength to the height of the first circuit member 30 and the second circuit member 40 is achieved, and the conductive particles 12 and the first and second circuits are electrically connected. The state in which the electrodes 32, 42 are surely in contact is maintained over a long period of time. The state of such a connection structure can be confirmed by observing the cross section of the connection u structure of the circuit member with an electron microscope. Further, in the state in which a transparent glass substrate is used as the circuit substrate, it can be confirmed by observing the surface of the circuit connecting portion through the glass substrate. Therefore, regardless of the presence or absence of the unevenness on the surface of the first and/or second circuit electrodes 32 and 42, the connection resistance between the first and second circuit electrodes 32 and 42 can be sufficiently reduced, and the first circuit electrode can be realized. 32 and the second circuit electrode 42 are electrically connected to each other well, and the long-term reliability of the electrical characteristics between the first and second circuit electrodes 3, 42 can be sufficiently improved. Further, in the above-described embodiment, the connection structure of the circuit member is manufactured using the film-like circuit connecting material 50. However, the film-like circuit connecting material 50 may be replaced with a circuit connecting material which will be described later. In this state, if the circuit connecting material is dissolved in a solvent and the solution is applied to any of the first circuit member 30 or the second circuit member 40 to be dried, it can be referred to as the first and the first. 2 between the circuit members 30, 40. Further, the film-like circuit connecting material 50 can be coated with the above-mentioned circuit connecting material by using a coating device (not shown) on a support (polyethylene terephthalate film or the like), and drying is predetermined. The hot air of time' and -33- 200939583 were produced. Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. [Production of Conductive Particles] (Preparation of Nuclei) Change the mixing ratio of tetramethylol methane tetraacrylate, divinylbenzene, and styrene monomer, and use phenylhydrazine peroxide as a polymerization initiator. Suspension polymerization. Next, by grading the obtained polymer, a core body having an average particle diameter of about 3 μηη is obtained. (Production of Conductive Particles No. 1) ❹ Electroless Ni plating treatment was performed on the surface of the core body to prepare conductive particles No. 1 having a Ni layer (metal layer) having a uniform thickness of 10 nm. (Production of Conductive Particles No. 2) An Au layer having a uniform thickness was formed by performing Au substitution plating on a conductive particle No. 1 at a thickness of 25 nm to prepare conductive particles N 〇 . -34- 200939583 (Production of conductive particles Νο·3) By adjusting the loading amount, processing temperature and time of the plating solution during the Ni plating treatment according to Japanese Patent No. 3696429, etc., the thickness of the plating is changed, and The surface of the aforementioned nucleus forms a protrusion of Ni plating. By this, a conductive particle having a target thickness of 180 to 210 nm, which also includes a raised Ni layer, is produced. Ν (3) 〇 (Production of conductive particles Νο·4) Au is performed on the conductive particles Νο. Instead of electroplating, an Au layer having a plurality of protrusions is formed to form conductive particles N 〇. In the case of the conductive particles No. 1 to 4 which were produced as described above, the height of the measurement protrusion and the distance between the adjacent protrusions were observed using an electron microscope (manufactured by Hitachi, Ltd., trade name "S-800"). ® . The material of the metal layer of each of the conductive particles, the Vickers hardness, the height of the protrusions, and the distance between the protrusions are shown in Table 1. -35- 200939583 [Table 1] Height of conductive metal layer protrusion (nm) Distance between protrusions (nm) Material thickness (nm) Vickers hardness No.1 Ni 100 700 No protrusion without protrusion No.2 Au/Ni 25/ 100 20/700 No protrusion and no protrusion No.3 Ni 90 700 100 700 No.4 Au/Ni 25/90 20/700 125 600 [Production of circuit connecting material] (Preparation of phenoxy resin solution) Phenoxy group 50 g of a resin (average weight molecular weight: 45,000, manufactured by UNION Carbide Co., Ltd., trade name "PKHC") was dissolved in a mixed solvent of toluene/ethyl acetate = 50/50 (mass ratio) to prepare a solid content of 40% by mass. a phenoxy resin solution. (Synthesis of urethane acrylate) Stirring polycaprolactone diol (average weight molecular weight: 800) 4 00 parts by mass, 131 parts by mass of 2-hydroxypropyl acrylate, and dibutyltin dilaurate as a catalyst 0.5 parts by mass of the ester and 1.0 part by mass of hydroquinone monomethyl ester as a polymerization inhibiting agent were simultaneously heated and mixed at 50 °C. Then, 22 parts by mass of isophorone diisocyanate was added dropwise to the mixed solution, and the mixture was stirred, and the temperature was raised to 80 ° C to carry out an ethyl carbamate reaction. After confirming that the reaction rate of the isocyanate group was 99% or more, the reaction temperature was lowered to obtain ethyl urethane acrylate. -36- 200939583 (Production of circuit connecting material A) 125 g of the above-mentioned phenoxy resin solution (solid content: 50 g), 49 g of the aforementioned urethane acrylate, glycerol acrylate lg, and The hardening agent which generates free radicals is heated to obtain 5 g of perhexylperoxy-2-ethylhexanoate to obtain an adhesive composition. The conductive connecting material was prepared by dispersing 2.3 parts by mass of the conductive particles No. 3 with respect to 100 parts by mass of the obtained adhesive composition. Next, using a coating apparatus, a film of a film having a thickness of 50 μm on one surface was coated, and the circuit connecting material was applied, and dried by a hot air of 7 μr for 3 minutes to form a film having a thickness of 18 μm on the PET film. The circuit is connected to the material Α. (Production of circuit connecting material B) A film-like circuit connecting material B having a thickness of ❹18 μm was produced except that 2.3 parts by mass of the conductive particles No. 1 was used instead of the conductive particles No. 3, and the rest was the same as the circuit connecting material a. * (Production of circuit connecting material C) - A film-like circuit connecting material having a thickness of 18 μm is produced in the same manner as the circuit connecting material a except that 2-1 mass parts of conductive particles Νο·2 are used instead of conductive particles Νο. c. (Production of circuit connecting material D) A film-like circuit connection having a thickness of 18 μm was produced in the same manner as the circuit connecting material A except that 2.1 parts by mass of the conductive particles Νο·4 was used instead of the conductive particles-37-200939583 sub No. Material D. (Example 1) A flexible wiring board having a two-layer structure composed of a polyimide film (thickness 38 μm) and a Sn-plated Cu foil (thickness 8 μη〇) (hereinafter referred to as FPC) is prepared as the first circuit member. In the FPC circuit, the line width is 18 μm and the pitch is 50 μm. Next, as the second circuit member, a glass substrate (thickness: 1.1 nm, surface resistance < 20 Ω) having a tantalum electrode circuit (thickness: 50 nm) is prepared. Mm) The circuit of the second circuit member has a line width of 2 5 μm and a pitch of 50 μm. Next, a circuit having a predetermined size (1.5 x 30 mm) is attached to the second circuit member. The connecting material A was heated and pressurized for 3 seconds under conditions of 70 ° C and 1.0 MPa, and temporarily joined. Then, after peeling off the PET film, FPC was placed and the FPC and the second circuit member were used. The circuit connecting material A is clamped, and the circuit of the FPC and the circuit of the second circuit member are aligned. Then, heating and pressurization are performed from above the FPC at 170 ° C, 3 MPa, and 10 seconds to connect the FPC. And the second circuit member. The circuit member is fabricated like this. (Example 2) The FPC of the first embodiment is prepared as the first circuit member. Next, as the second circuit member, it is prepared to have ιζο (outside 200939583 layer, thickness 50 nm) /Cr (on the surface). a glass substrate (thickness l"mm) of a three-layer structure circuit electrode (surface resistance < 20 Ω) having a thickness of 20 nm) / A1 (thickness: 100 nm). The circuit of the second circuit member has a line width of 25 μm and Then, the connection structure of the circuit member was made using the circuit connecting material A in the same manner as in the first embodiment. (Example 3) 0 The FPC similar to that of the first embodiment was prepared as the first circuit member. A glass substrate (thickness: 1.1 mm) of a circuit electrode (surface resistance < 20 Ω) having a two-layer structure of ITO (outermost layer, thickness: 50 nm) / Cr (thickness: 200 nm) on the surface was prepared as the second circuit member. The circuit of the second circuit member has a line width of 25 μm and a pitch of 50 μm. Then, a circuit connecting material Α is used in the same manner as in the first embodiment to fabricate a connection structure of the circuit member. Q (Example 4) Preparation is the same as the implementation example 1 FPC is used as the first circuit member. Next, as the second circuit member, ITO (outermost layer, thickness 50 nm) / Ti (thickness 100 nm) / A1 (thickness 200 nm) / Ti (thickness l) is prepared on the surface.玻璃nm) A glass substrate (thickness 1.1 mm) of a circuit electrode (surface resistance < 20 Ω) of a 4-layer structure. The circuit of the second circuit member has a line width of 25 μm and a pitch of 50 μm. Next, the circuit connecting material A was used in the same manner as in the first embodiment to fabricate a connection structure of the circuit member. -39-200939583 (Example 5) An FPC similar to that of Example 1 was prepared as the first circuit member. Next, as the second circuit member, a glass substrate (thickness: 1.1 mm) having an A1 circuit electrode (thickness: 200 nm, surface resistance < 5 Ω) on the surface was prepared. The circuit of the second circuit member has a line width of 25 μm and a pitch of 50 μm. Next, the circuit connection material A was used in the same manner as in the first embodiment to fabricate the connection structure of the circuit member.比较 (Comparative Example 1) The connection structure of the circuit member was produced in the same manner as in Example 1 except that the circuit connecting material B was used instead of the circuit connecting material A. (Comparative Example 2) The connection structure of the circuit member was produced in the same manner as in Example 2 except that the circuit connecting material B was used instead of the circuit connecting material a.比较 (Comparative Example 3) A connection structure of a circuit member was produced in the same manner as in Example 3 except that the circuit connecting material B was used instead of the circuit connecting material a. (Comparative Example 4) A connection structure of a circuit member was produced in the same manner as in Example 4 except that the circuit connecting material B was used instead of the circuit connecting material a. -40-200939583 (Comparative Example 5) The connection structure of the circuit member was produced in the same manner as in Example 5 except that the circuit connecting material B was used instead of the circuit connecting material A. (Comparative Example 6) The connection structure of the circuit member was produced in the same manner as in Example 1 except that the circuit connecting material C was used instead of the circuit connecting material A.比较 (Comparative Example 7) A connection structure of a circuit member was produced in the same manner as in Example 2 except that the circuit connecting material C was used instead of the circuit connecting material A. (Comparative Example 8) A connection structure of a circuit member was produced in the same manner as in Example 3 except that the circuit connecting material C was used instead of the circuit connecting material A. ❹ (Comparative Example 9) • The connection structure of the circuit member was produced in the same manner as in Example 4 except that the circuit connecting material C was used instead of the circuit connecting material A. (Comparative Example 1 〇) The connection structure of the circuit member was produced in the same manner as in Example 5 except that the circuit connecting material C was used instead of the circuit connecting material A. -41 - 200939583 (Comparative Example 11) A connection structure of a circuit member was produced in the same manner as in Example 1 except that the circuit connecting material D was used instead of the circuit connecting material A. (Comparative Example 1 2) The connection structure of the circuit member was produced in the same manner as in Example 2 except that the circuit connecting material D was used instead of the circuit connecting material a. (Comparative Example 1 3) The connection structure of the circuit member was produced in the same manner as in Example 3 except that the circuit connecting material D was used instead of the circuit connecting material a. (Comparative Example 1 4) The connection structure of the circuit member was produced in the same manner as in Example 4 except that the circuit connecting material D was used instead of the circuit connecting material a. ❹ (Comparative Example 1 5) The connection structure of the circuit member was produced in the same manner as in Example 5 except that the circuit connecting material D was used instead of the circuit connecting material a. [Measurement of the connection resistance] The first circuit component (FPC) is measured using a universal electric meter (manufactured by ADC Co., Ltd., trade name "analog-type universal electric meter 7461 a") for the connection structure of the above-mentioned circuit member. ) The circuit electrode and the second circuit -42 - 200939583 The connection resistance between the circuit electrodes of the component 値. The connection resistance was measured in the initial stage (after the connection) and after maintaining the temperature in a constant temperature and humidity chamber of 80 ° C and 95 % RH for 500 hours (high temperature and high humidity treatment). The results are shown in Table 2. In Table 2, the connection resistance 表示 is expressed by the sum of the resistances of the adjacent resistors of 3 7 points and the standard deviation of 3 times (χ + 3σ ). In addition, the rate of increase in resistance is expressed as a percentage to show the increase in resistance 由 from the initial resistance 値 to the high temperature and high humidity treatment, specifically by the following formula: resistance increase rate (%) = [(after treatment) Resistance 値 - initial resistance 値) / initial resistance 値] xlOO. The effect of improving the connection reliability is judged by a resistance increase rate of less than 1 〇 ° /. It has an improvement effect, and it is a level of 10% or more and less than 20%, and it is 20% or more, and there is no improvement effect. [Number of Conductive Particles Present on Circuit Electrode] Q Calculated by visual observation using a differential interference microscope = 38) The number of conductive particles present on the respective circuit electrodes of the connection structure of the above-mentioned circuit member. As a result, in the circuit electrodes of Examples 1 to 15 and Comparative Examples 1 to 25, the average number of conductive particles was in the range of 32 to 45, and no electric conduction due to the difference in circuit connecting material or circuit member was observed. Extreme increase or decrease in the number of particles. -43- 200939583 [Table 2] Circuit connection material Conductive particles 2nd circuit electrode connection resistance (Ω) Resistance increase rate (%) No. The outermost layer has protrusions after initial treatment Example 1 ΙΤΟ Circuit 117.3 124.7 6.3 Example 2 IZO/ Cr/Al job 85.6 91.2 6.5 Example 3 A 3 Ni with ITO/Cr job 67.3 72.3 7.4 Example 4 ITO/Ti/Al/Ti Fu 68.5 73.6 7.4 Example 5 AlSgg 23.1 23.9 3.5 Comparative Example 1 ITO circuit 126.3 163.4 29.4 Comparative Example 2 IZO/Cr/Al circuit 92.6 117.2 26.6 Ratio _3 B 1 Ni Μ ITO/Cr circuit 68.4 94.7 38.5 Comparative Example 4 ITO/Ti/Al/Ti circuit 71.1 96.0 35.0 Comparative Example 5 A1 circuit 26.0 34.9 34.2 Comparative example 6 ITO circuit 116.4 140.8 21.0 Comparative Example 7 IZO/Cr/Al circuit 86.2 103.3 19.8 Comparative Example 8 C 2 Au No ITO/Cr circuit 66.7 83.4 25.0 Comparative Example 9 ITO/Ti/Al/Ti circuit 66.8 81.1 21.4 Comparative Example 10 Aim 23.9 27.5 15.1 Comparative Example 11 ITO from 118.7 135.2 13.9 Comparative Example 12 IZO/Cr/Al circuit 85.8 99.4 15.9 Comparative Example 13 D 4 Au ITO/Cr circuit 70.4 82.2 16.8 Comparative Example 14 ITO/Ti/Al/Ti circuit 65.5 77.3 18.0 Comparative example 15 A1 circuit 22.4 23.2 3.6 As shown in Table 2, in the state where the second circuit member which constitutes the whole or the surface of the circuit electrode by ITO or IZO is used, The connection structure of the circuit members of Examples 1 to 4 gave a so-called very small result when the resistance increase rate was less than 7.5%. On the other hand, the resistance increase ratio of the connection structures of Comparative Examples 1 to 4 was about 27 to 39%, and the resistance increase ratio of the connection structures of Comparative Examples 6 to 9 was about 2 〇 to 25%, Comparative Example i丨~ 〗 4 connection 200939583 structure of the resistance increase rate is about 14 to 18%. From this, it is known that a circuit connecting material having conductive or magnetic particles having a protrusion and including a metal layer or a metal layer as a conductive layer of Ni is formed with respect to a circuit electrode which constitutes the entire or surface of the circuit electrode by ITO and IZO, Used for connections and found improvements in connection reliability. Further, in the state of using the second circuit member having the A1 circuit electrode, the resistance increase rate was obtained in Example 5 and Comparative Example 15 in which the circuit connection material including the conductive particles having the protrusions was connected to II. The result is reduced to approximately 3.5%. This result is considered to be that when the connection is made, the protrusion on the surface of the conductive particle penetrates the oxide film on the surface of the electrode of the A1 circuit and contacts the electrode of the circuit. On the other hand, in Comparative Examples 5 and 10 in which the material was connected by a circuit connecting material containing no protruding conductive particles, the resistance increase rate of Comparative Example 10 was about 34%, and the resistance increase rate of Comparative Example 15 was It is about 15%. Further, the ratio of the use of the fifth embodiment using the conductive particles having the protrusions and the metal layer being Ni and the use of the conductive particles having the protrusions and the outermost layer of Au is the same as that of the example 15 and thus A1 constitutes a circuit member of the circuit electrode, and the effect of improving the connection reliability due to the difference in the metal layer of the outermost layer of the conductive particles tends to be inconspicuous. Further, the cross-section of the connection structure of the circuit members produced in Examples 1 to 5 was observed by a scanning electron microscope (SEM), and it was confirmed that the metal layer of the inner portion of the protruding portion of the metal layer constituting the conductive particles was embedded. To the nuclear body. A cross-sectional SEM photograph of the joint portion of the connection structure of the circuit member produced in the second embodiment is shown in Fig. 4 as an example. -45- 200939583 It is confirmed from the above that, by the connection structure of the circuit member of the present invention, it is possible to achieve a good electrical connection between the opposing circuit electrodes, and at the same time, even in a high-temperature and high-humidity environment or thermal shock Tests and the like can also sufficiently improve the reliability of the stable connection. [Industrial Applicability] When the material is connected by the circuit of the present invention, a good electrical connection between the opposing circuit electrodes can be achieved, and at the same time, the electrical characteristics between the high circuit electrodes can be sufficiently improved. reliability. Further, according to the present invention, it is possible to provide a connection structure of a circuit member which is sufficiently excellent in long-term reliability of electrical characteristics between circuit electrodes, and a connection method therefor. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a connection structure of a circuit member of the present invention. Fig. 2 is a cross-sectional view showing various forms of conductive particles constituting the circuit connecting material of the present invention. Fig. 3 is a cross-sectional view showing an embodiment of a film-like circuit connecting material of the present invention. Fig. 4 is a cross-sectional SEM photograph of the joint portion of the joint structure of the circuit member produced in the second embodiment. [Explanation of main component symbols] H: Protrusion height of conductive particles -46 - 200939583 S : Adjacent distance between protrusions 1: Connection structure of circuit members 10 : Circuit connection member 11 : Insulating material 12 : Conductive particles 14 : Protrusions (protrusions 21) Core (particle) © 21a : Core part (nuclear body) 21b : Projection part 22 : Metal layer 30 : First circuit member 3 1: Circuit board (first circuit board) 3 1a : Main surface 32 : Circuit electrode (first circuit electrode) 40 : Second circuit member 0 41 : Circuit board (second circuit board) 4 1a : Main surface 42 : Circuit electrode (second circuit electrode) 50 : Membrane circuit connecting material 51 : Adhesive Agent composition-47-

Claims (1)

200939583 X. Patent application: 1. A circuit connecting material, which is a circuit connecting material used for forming two circuit members of a circuit electrode, and electrically connecting the circuit electrodes in opposite directions, and is characterized in that it contains an adhesive. a composition, a conductive particle, a core body formed of an organic polymer compound, and a metal layer covering the core body, wherein the metal layer has a protrusion protruding toward an outer side of the conductive particle, and the metal layer is made of nickel or nickel In the alloy structure, when a pressure is applied to the conductive particles, a metal layer of an inner portion of the protruding portion is fitted into the core body. 2. The circuit connecting material of claim 1, wherein the metal layer has a Vickers hardness of 400 to 1000. 3. A circuit connecting material which is a circuit connecting material used for forming two circuit members of a circuit electrode to electrically connect the circuit electrodes, and is characterized in that it contains an adhesive composition and conductive particles. The conductive particle includes a core body formed of an organic polymer compound and a plurality of metal layers covering the core body. The metal layer has a protrusion protruding toward the outside of the conductive particle, and the outermost layer of the metal layer is made of nickel or a nickel alloy. When the pressure is applied to the conductive particles, the metal layer of the inner portion of the protrusion is embedded in the core body. 4. For the circuit connection material of claim 3, wherein the outermost layer of the metal layer of the former -48-200939583 has a Vickers hardness of 400 〜1 0 0 〇5. a structure comprising: a circuit connecting member formed by forming a circuit electrode, wherein the circuit electrode is opposed to each other, and a circuit connecting member interposed between the circuit member and electrically connected to the circuit electrode after being heated and pressurized The circuit connecting member is a cured material of the circuit connecting material according to any one of claims 1 to 4, wherein the metal layer is embedded in an inner portion of the protruding portion of the conductive particles contained in the circuit connecting material. The connection structure of the circuit member according to claim 5, wherein at least one surface of the circuit electrodes of the two circuit members is made of indium-tin oxide. 7. The connection structure of the circuit member according to the fifth or sixth aspect of the invention, wherein the Q surface of at least one of the circuit electrodes of the two circuit members is made of indium-zinc oxide. 8. A method of connecting circuit members, characterized in that a circuit, an electrode, and two circuit members arranged to face the circuit electrodes are interposed between any one of items 1 to 4 of the patent application scope. The circuit connecting material of the item is electrically and pressure-bonded to the metal layer of the inner portion of the protruding portion of the conductive particles contained in the circuit connecting material, and is embedded in the core body to electrically connect the circuit electrodes. -49 -