TW200946629A - Circuit connecting material and structure for connecting circuit member - Google Patents

Abstract

A circuit connecting material is arranged between a first circuit member (30) having a first circuit electrode (32), and a second circuit member (40), which faces the first circuit member (30) and has a second circuit electrode (42), and the circuit connecting material electrically connects the first circuit electrode (32) and the second circuit electrode (42) with each other. The circuit connecting material contains an adhesive composition and conductive particles (12) having a diameter of 0.5-7[mu]m. An outermost layer (22) of the conductive particle (12) is composed of a metal having a Vickers hardness of 300Hv or more, a part of the outermost layer (22) protrudes outward to form a protruding section (14), and the diameter and the hardness of the conductive particle (12) are in a specific relation.

Description

200946629 IX. Description of the Invention [Technical Field] The present invention relates to a connection structure of a circuit connecting material and a circuit member. [Prior Art]

The connection between the liquid crystal display and the tape carrier package (Tape Carrier Package: TCP '), the connection between the flexible printed circuit (FPC 0 ) and the TCP, or the connection between the FPC and the printed wiring board, when the circuit components are connected to each other, A circuit connecting material in which an electrically conductive particle is dispersed in an adhesive (for example, an isotropic conductive adhesive). Further, recently, when a semiconductor wafer is mounted on a substrate, the semiconductor germanium wafer is directly mounted on the substrate for the purpose of connecting the circuit members to each other without using wiring, and the flip chip is packaged. In the flip chip package, when the circuit members are connected to each other, a circuit connecting material such as an anisotropic conductive adhesive is used (see, for example, Patent Documents 1 to 5). 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Patent Document 5] JP-A-2001-189171 [Patent Document 6] JP-A-2005-166438 (Summary of the Invention) [Disclosed by the Invention] -5-200946629 [Problems to be Solved by the Invention] Since the size and thickness of the electronic device are reduced, the circuit formed by the circuit member is increased in density, and the distance between adjacent electrodes or the width of the electrode tends to be extremely narrow. The circuit electrode is formed by forming a metal which is a basic circuit in the entire substrate, applying a photoresist to the circuit electrode portion to be cured, and other portions are formed by acid or alkali etching. However, the above-mentioned high-density circuit has a comprehensive substrate. When the unevenness of the formed metal is large, the concave portion and the convex portion are different in etching time, and precise etching cannot be performed, and there is a problem that a short circuit or a disconnection occurs between adjacent circuits. Therefore, the metal of the high-density circuit (the surface of the circuit electrode) is expected to have a small unevenness, that is, the surface of the electrode is flat. However, when the circuit electrodes having a flat surface are opposed to each other with a connection between the conventional circuit connecting materials, the adhesive resin remains between the conductive particles contained in the circuit connecting material and the flat circuit electrodes, so that the conductive particles and the circuit electrodes are interposed. Insufficient contact, there is a problem that sufficient electrical connection and long-term reliability of electrical characteristics cannot be ensured between circuit electrodes. Therefore, in order to ensure long-term reliability of electrical connection and electrical characteristics between circuit electrodes, it is proposed to provide a plurality of protrusions on the surface of the conductive particles, and to form a protrusion between the conductive particles and the circuit electrodes when the circuits are connected. The adhesive composition is such that the conductive particles are in contact with the circuit electrode (see Patent Document 6 above). However, even with this method, the specifications (materials, etc.) of the circuit electrodes may have a small effect of ensuring long-term reliability of electrical connection and electrical characteristics between circuit electrodes. The present invention has been made in view of the above circumstances, and the object of the present invention is -6-200946629 to provide a good electrical connection between opposing circuit electrodes even when the surface of the circuit electrode is flat, and at the same time, the circuit electrodes can be sufficiently improved. The connection structure of the circuit connecting material and the circuit member for the long-term reliability of the electrical characteristics. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have found that the reason why the circuit connection materials are not sufficiently ensured the electrical connection between the circuit electrodes and the long-term reliability of the electric Q characteristics is the conductive particles. The material of the outermost layer. In other words, the present inventors have found that the outermost layer of the conductive particles contained in the conventional circuit connecting material is composed of a soft metal Au, and therefore, even if the protruding portion of Au formed on the surface of the conductive particles penetrates between the conductive particles and the circuit electrode With the composition of the subsequent agent, the protrusion of Au is also deformed so as to be buried in the circuit electrode. The inventors have found that changing the outermost layer material of the conductive particles to a harder metal than Au, and matching the particle size of the conductive particles to optimize the hardness of the conductive particles, can improve the electrical connection and electrical characteristics between the circuit electrodes for a long time. Q relies on the nature to complete the present invention. The circuit connecting material of the present invention is interposed between the first circuit member having the first circuit electrode and the second circuit member having the second circuit electrode facing the first circuit member, and the first circuit electrode and the first circuit electrode 2 circuit connection material for electrical conduction, comprising an adhesive composition and conductive particles having a diameter of 0.5 to 7 μm, and the outermost layer of the conductive particles is composed of a metal having a Vickers Hardness of 300 Ην or more. One of the outermost layers protrudes from the outside to form a protrusion, and the diameter of the conductive particles is 5 μm or more, and when the thickness is 7 μm or less, the hardness of the conductive particles is 200 200946629 to 1 200 kgf/mm 2 2 , and the diameter of the conductive particles is 4 μm or more, and When the thickness is less than 5μηι, the hardness of the conductive particles is 300 to 1300 kgf/mm2, the diameter of the conductive particles is 3 μm or more, and when the thickness is less than 4 μm, the hardness of the conductive particles is 400 to 1 400 kgf/mm 2 , and the diameter of the conductive particles is 2 μm or more. When the thickness is less than 3 μm, the hardness of the conductive particles is 450 to 1 700 kgf/mm 2 , the diameter of the conductive particles is 0.5 μm or more, and when it is less than 2 μm, the conductivity is The hardness of the particles is 5 0 0 to 2 0 0 0 kgf / mm 2 ° The hardness range of the conductive particles of the present invention is defined by the above unit, and is converted into the current mainstream SI unit, 200 to 1200 kg f/mm 2 is 1.96 1 - 1 After 1.768GPa, 3 0 0 ~ 1 3 0 0 kgf/mm2 is 2.942 ~ 1 2.749GPa, 400 ~ 1 40Okgf / mm2 is 3.923 1 3.729GPa, 450~ 1 70 Okgf / m The m2 system becomes 4.413 1 6.67 1 GPa, and the 500~2000kgf/m m2 system becomes 4.93 -8- 1 9.6 1 3 GPa. In the present invention, the hardness of the conductive particles is optimized in accordance with the diameter of the conductive particles, and a part of the outermost layer composed of a metal having a Vickers Hardness of 300 Hv or more protrudes outward. Since the protrusions are formed, when the first and second circuit members are pressed, the protrusions are deeply buried in the first and second circuit electrodes, and the conductive particles are formed to be moderately flat. As a result, the contact area between the circuit and each of the conductive particles is increased, and the circuit members are in contact with each other in a state where the conductive particles are surely in contact with the first and second circuit electrodes, so that the connection resistance between the electrodes is small and maintained for a long period of time. . In other words, a good electrical connection between the opposing circuit electrodes can be achieved, and the long-term reliability of the electrical characteristics between the circuit electrodes can be sufficiently improved. Conductive 200946629 Particle formation "flat" guides the electrical particles to the surface of the circuit electrode, the direction of the vertical is not formed, but is skewed in a slightly parallel direction. In the above-mentioned circuit connecting material of the present invention, the height of the projections is 50 to 5,000 nm, and the outermost portion is partially protruded from the outer side, and the distance between the projections adjacent to the plurality of projections is preferably 100 nm or less. When the height of the protrusion is less than 5 Onm, the connection structure of the first circuit member and the second circuit member of the circuit connecting material is high-temperature and high-humidity treatment, and the connection resistance tends to become high. When the height is more than 500 nm, the conduction is high. Since the contact area between the particles and the first and second circuit electrodes is small, the connection resistance 倾向 tends to be high. In the above circuit connecting material of the present invention, the outermost layer is preferably composed of Ni. The effect of the present invention is easily obtained by forming the outermost layer of a metal Ni having a Vickers hardness of 3 ΟΟΗν or more. The above circuit connecting material of the present invention is preferably in the form of a film. In the connection structure of the circuit member of the present invention, the circuit connecting material is interposed between the first circuit member and the second circuit member to electrically conduct the first circuit electrode and the second circuit electrode. The connection structure of the circuit member using the circuit connecting material of the present invention is maintained for a long period of time in which the connection resistance between the first and second electrodes is small. In other words, a good electrical connection between the opposing circuit electrodes can be achieved, and the long-term reliability of the electrical characteristics between the circuit electrodes can be sufficiently improved. In the connection structure of the circuit member of the present invention, the first or second circuit electrode is preferably an indium-tin oxide or an indium-zinc oxide. -9 - 200946629 In the present invention, when the circuit electrode is composed of indium-tin oxide or indium-zinc oxide, the effect of improving the electrical connection between the electrode electrodes and the long-term reliability of the electrical characteristics is remarkable. In the connection structure of the circuit member of the present invention, the thickness of the first or second circuit electrode is preferably 50 nm or more. When the thickness of the first or second circuit electrode is less than 5 Onm, when the circuit members are pressed against each other, the protruding portion on the surface of the conductive particles contained in the circuit connecting material penetrates the first or second circuit electrode, possibly contacting the circuit member. The contact area between the first or second circuit electrode and the conductive particles is reduced, and the connection resistance tends to increase. [Effects of the Invention] According to the connection structure of the circuit connecting material and the circuit member of the present invention, even if the surface of the circuit electrode is flat, a good electrical connection between the opposing circuit electrodes can be achieved, and the circuit electrodes can be sufficiently improved. Long-term reliability of electrical properties. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and the description thereof will not be repeated. Moreover, the figure is shown on the expedient, and the dimensional ratio of the drawing is not necessarily consistent with the description. [Circuit Connection Material] -10-200946629 The circuit connecting material of the present invention contains an adhesive composition and conductive particles, but the form thereof is, for example, a paste or a film. Hereinafter, a film-like circuit connecting material of an embodiment of the circuit connecting material of the present invention will be described in detail. The film-like circuit connecting material is formed by forming a circuit connecting material into a film shape. For example, a circuit connecting material can be applied to a support (PET (polyethylene terephthalate) film or the like) using a coating device. It is made by '* hot air drying at a predetermined time. The φ film-like circuit connecting material contains the conductive particles 1 and the adhesive composition. The adhesive composition has adhesiveness and is hardened by a hardening treatment (see Figs. 1 and 2). As a result, the film-like circuit connecting material is interposed between the first and second circuit members 30 and 40, and the first circuit electrode 32 of the second circuit member 3 and the second circuit electrode of the second circuit member 40 are provided. 42 produces electrical conduction. Since the film-like circuit connecting material is in the form of a film and is easy to handle, when the first circuit member 30 and the second circuit member 40 are connected, it is easy to be interposed between the structures, and the first circuit member 30 and the second circuit member can be easily formed. 40 connection operation. (Electrically conductive particles) The conductive particles 12 contained in the film-like circuit connecting material are as shown in Fig. 2 (a), and the core body 21 generally formed of an organic polymer compound and the outermost layer formed on the surface of the core body 21 The metal layer 22 is formed, which is advantageous for the conductive particles to form protrusions. The core body 21 is constituted by a core side protrusion 21b formed on the surface of the core portion 21a and the core portion 21a. -11 - 200946629 The core body 21 can be formed by adsorbing a plurality of core side protrusions 21b having a smaller diameter than the core portion 21a due to the surface of the core portion 21a. A portion of the metal layer 22 protrudes from the outside to form a plurality of protrusions 14. The metal layer 22 is made of a metal having conductivity and a Vickers hardness of 3 ΟΟΗν or more. In the present invention, the diameter of the conductive particles is 0.5 μm or more and 7 μm or less. When the diameter is less than 0.5 μm, there is a tendency that a good conduction is not obtained. When the diameter exceeds 7 μm, a short circuit tends to occur when the distance between the electrodes such as the liquid crystal panel is short. The diameter of the conductive particles refers to the particle diameter of the entire conductive particles 12 having the protrusions 14 and can be measured by an electron microscope. When the diameter of the conductive particles is 5 μηη or more and 7 μm or less, the hardness of the conductive particles is 200 to 1 200 kgf/ Mm2 ( 1 · 9 6 1 ~ 1 1.7 6 8 GP a ) ° The diameter of the conductive particles is 4 μm or more. When the thickness is less than 5 μm, the hardness of the conductive particles is 300 to 1300 kgf/mm 2 ( 2.942 〜1 2.749 GPa). The diameter of the conductive particles is 3 μm or more, and when the thickness is less than 4 μm, the hardness of the conductive particles is 400 to 14001 ^ by 111 «12 ( 3.923 to 13.729 ??). The diameter of the conductive particles is 2 μm or more, and when it is less than 3 μm, the hardness of the conductive particles is 450 to 1700 kgf/mm 2 (4.413 to 16_671 GPa). The diameter of the conductive particles is 0.5 μm or more, and when the thickness is less than 2 μη, the hardness of the conductive particles is 500 to 2 0 0 0 gf/mm 2 (4.9 0 3 to 1 9 6 1 3 GP a ). In the present embodiment, the diameter of the conductive particles 12 is adjusted to optimize the hardness of the conductive particles 12 as described above, and one of the outermost layers of the metal having a Vickers hardness of 300 Hv or more protrudes from the outer side to form a protrusion. A good electrical connection between the opposing circuit electrodes 32, 42 can be achieved -12-200946629, and the reliability between the circuit electrodes 32, 42 can be sufficiently improved. The diameter of the conductive particles 12 and the electrical connection and electrical relationship between the path electrodes 32 and 42 will be described below. Electrically connecting the opposite circuit with the circuit connecting material, the connection resistance is based on the number of circuit electrodes 32, 12 and the circuit electrode and each of the conductive particles 1, the contact area is due to the flatness of the conductive particles 12, exists at the circuit electrode 32, The lower the connection resistance of the conductive particles of 42 is, the larger the contact area between the flattening ratios 32 and 42 of the conductive particles 12 and the conductive particles 12 is, and the more the unit volume of the circuit connecting material is, the more the circuit electrodes 32 and 42 are present. Between; 5 more. The smaller the diameter of the conductive particles 12, the more the number of conductive particles 12 contained in the electric volume is 42 and the contact, which contributes to the number of circuit electrodes 32, 42 between the electrodes 32, 42 of the surface electrodes 32, 42 , 42 is in contact with each of the conductive particles 12. The smaller the flatness ratio of the connection of the circuit electrodes 32, 42 and the conductive particles 12, the narrower. Conductive particle 1 depends on the hardness of the electric particle 12, when the conductive particle 12 is smaller than 0, when the diameter of the conductive particle 12 is small, the greater the degree, the long-term hardness of the electrical property of the connection between the circuit members 30, 40 and The contact area between the protrusions and the electrode 32' 42 of the long-term reliability of the electrical property changes between 42 and 42. In other words, the greater the number of 12 12 , the larger the circuit electrode connection resistance is. One of the conductive particles 1 : The unit of the connecting material of the conductive particles 1 2 . The conductive grain size of the electrical connection with the circuit electrode 32 is limited. Therefore, the narrower the circuit area, the more the contact area is, the flatness of the conductive particles 2 is greater, and the harder the conductive particles 12 are. The smaller the tendency -13 to 200946629, the larger the diameter of the conductive particles 12 is, the smaller the number of the conductive particles 12 existing between the circuit electrodes 32 and 42 is. Therefore, in order to reduce the connection resistance between the circuit members 30 and 40, it is necessary to reduce the connection resistance between the circuit members 30 and 40. The contact area between the circuit electrodes 32, 42 and the respective conductive particles 12 is enlarged. The larger the flatness ratio of the conductive particles 12, the larger the contact area between the circuit electrodes 32, 42 and the respective conductive particles 12. The smaller the hardness of the conductive particles, the larger the flatness of the conductive particles 12. As described above, when the particle diameter of the conductive particles 12 is large, the hardness of the conductive particles 12 is smaller, and the connection resistance between the circuit members 30 and 40 tends to be small. As described above, the hardness of the conductive particles which can obtain good connection resistance between the circuit members 30 and 40 varies depending on the diameter of the conductive particles 12. Therefore, in the present embodiment, by using the conductive particles 12 whose diameter and hardness of the conductive particles 12 satisfy the above relationship, a good connection resistance can be obtained even after a reliability test such as a high temperature and high humidity test. When the hardness of the conductive particles 12 is lower than the lower limit 硬度 of the hardness corresponding to the diameter of each conductive particle, the restoring force of the conductive particles 12 is weak, and the connection resistance tends to increase after the reliability test such as the high temperature and high humidity test. Further, when the hardness of the conductive particles 12 is higher than the upper limit 硬度 of the hardness corresponding to the diameter of each of the conductive particles, the conductive particles 12 are not sufficiently flat, and therefore the contact area between the conductive particles 12 and the circuit electrodes 32 and 42 is reduced. After the reliability test such as the high temperature and high humidity test, the connection resistance tends to increase. Further, since the metal layer 22 made of a metal having a Vickers hardness of 300 Hv or more is harder than the outermost layer made of Au, the protruding portion 14 protruding from the metal layer 22 is more likely to be buried than in the related art. In the circuit electrode 32 - 14 - 200946629 '42, the contact area of the conductive particles 12 with the circuit electrodes 32, 42 is increased. By the hardening treatment, the circuit connecting material can keep the conductive particles 12 in contact with the circuit electrodes 32 and 42 for a long period of time, and sufficiently ensure the state of the contact area between the conductive particles 12 and the circuit electrodes 32 and 42. An organic polymer compound constituting the core portion 21a of the core body 21, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyl resin, a polybutadiene resin, or the like, You can also use these exchanges. The average particle diameter of the core portion 2 1 a in the core body 2 1 is preferably 〇 5 or more and 7 μπι or less. The organic polymer compound constituting the core-side protrusion 21b of the core body 21 is, for example, an acrylic resin, a styrene resin, a benzoguanamine tree, a polyoxymethylene resin, a polybutadiene resin, or the like. You can also use these cross-linkers. The organic polymer compound constituting the core side protrusion portion 21b may be the same as or different from the organic molecule compound constituting the core portion 21a. The average particle diameter of the core side protrusion portion .21b is preferably 50 to 500 ηηι. The hardness of the conductive particles 12 is almost dominated by the hardness of the core body 21 of the conductive particles 12. The hardness of the conductive particles 12 depends on the structure of the molecules constituting the core body 21 and the distance between the crosslinking points and the degree of crosslinking. A linear structure such as benzoguanamine has a straight structure, and its distance between cross-linking points is also short. Therefore, the higher the proportion of benzoguanamine or the like which is formed in the whole molecule constituting the core body 21, the harder it is. The conductive particles 12', in turn, increase the degree of crosslinking of the core body 21 of the conductive particles 12 to obtain hard conductive particles 12. Since the distance between the cross-linking points is constant, the acrylic acid ester, the diallyl phthalate ester, and the like become acrylate, diallyl phthalate, etc. which are contained in the whole molecule of the core body 21. The higher the ratio, the softer the conductive particles 12 are obtained, and the lower the degree of crosslinking of -15-200946629, the soft conductive particles 12 can be obtained. The metal layer 22 is made of a metal having a Vickers hardness of 3 ΟΟΗν or more, for example, Cu, Ni or a Ni alloy, Ag or an Ag alloy, and more preferably Ni. The metal layer 22 can be formed by, for example, plating a metal having a Vickers hardness of 3 ΟΟΗν or more with respect to the core body 21 by electroless plating. The thickness of the metal layer 22 (thickness of plating) is preferably from 50 to 170 nm, more preferably from 50 to 150 nm. When the thickness of the metal layer 22 is in this range, the connection resistance between the circuit electrodes 32, 42 is apt to be further lowered. When the thickness of the metal layer 22 is less than 50 nm, plating defects or the like tend to occur, and the connection resistance tends to become large. When the thickness exceeds 17 Å, condensation occurs between the conductive particles, and a short circuit tends to occur between adjacent circuit electrodes. Further, the thickness of the metal layer 22 means the average thickness of the metal layer 22 from which the protrusions 14 are removed. The height Η of the protrusions 14 is preferably from 50 to 500 nm, more preferably from 75 to 300 nm. When the height of the protrusions is less than 50 nm, the connection resistance tends to become high after the high-temperature and high-humidity treatment. When the thickness is more than 500 nm, the contact area between the conductive particles 12 and the circuit electrodes 32 and 42 becomes small, and thus the connection resistance varies. High tendency. The distance S between the adjacent projections 14 is preferably 1 〇〇〇 nm or less, and more preferably 50 Å or less. Further, the distance S between the adjacent protruding portions 14 is such that the adhesive composition does not enter between the conductive particles 12 and the circuit electrodes 32 and 42. When the conductive particles 12 are sufficiently in contact with the circuit electrodes 32 and 42, at least 50 nm or more. Preferably. 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. Specifically, 'Adjustment-16-200946629 The magnification of the electron microscope is such that there are more than 10,000 conductive particles in the field of view, and the height of the protrusions and the adjacent protrusions for the arbitrarily selected three conductive particles. The distance between the two points was measured at 5 points 'the average 値 of the obtained 15 data. The amount of the conductive particles 12 of the film-like circuit connecting material is preferably 0.1 to 30 parts by volume for the adhesive composition, and the amount of the conductive particles can be used separately depending on the application. The amount of the conductive particles 12 is preferably from 0.1 to 10 parts by volume from the viewpoint of preventing short circuit of the φ circuit electrodes 32, 42 due to excessive conductive particles 12. The conductive particles 12 are as shown in Fig. 2(b), and the core body 21 can be constituted only by the intermediate core portion 21a. The conductive particles 12 are obtained by metallizing the surface of the core body 21 and forming a metal layer 22 on the surface of the core body 21. The protrusions 14 can be formed by changing the plating conditions and changing the thickness of the metal layer 22 due to metal plating. For example, a plating solution having a higher concentration is added to the plating solution to be used first, and the plating solution concentration is made uneven to change the plating conditions. (Adhesive composition) The adhesive composition contained in the film-like circuit connecting material is preferably a composition containing a latent curing agent of an epoxy resin and an epoxy resin (hereinafter referred to as "first composition"), A composition containing a radical-binding substance and a curing agent that generates free radicals by heating (hereinafter referred to as "second composition") or a mixed composition of the first composition and the second composition. The epoxy resin contained in the first composition includes, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type -17-200946629 epoxy resin, Phenolic novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, B-type epoxy resin, trimeric isocyanate type epoxy resin, aliphatic chain epoxy resin. These epoxy resins can be halogenated or hydrogenated. These epoxy resins can be used in combination of two or more kinds. The latent curing agent contained in the first composition may be any one that cures the epoxy resin. Such a latent curing agent is, for example, an anionic polymerizable catalyst-type curing agent or a cationic polymerizable catalyst-type curing agent. Agent, addition polymerization type hardener. These can be used individually or in mixture of 2 or more types. Among them, it is excellent in the quick-curing property, and it is preferably an anionic or cationically polymerizable catalyst-type hardener from the viewpoint of not requiring chemical equivalent. An anionic or cationically polymerizable catalyst-type hardener, for example, an imidazole-based, an anthraquinone-based, a boron trifluoride-amine complex, a phosphonium salt, an amine imine, a diamine maleedonitrile, a melamine and A derivative such as a derivative, a salt of a polyamine, a dicyanodiamine or the like can also be used. The addition polymerization type hardener is, for example, a polyamine, a polythiol, a polyphenol, an acid anhydride or the like. When a tertiary amine or an imidazole is blended as an anionic polymerization type catalyst type hardener, the epoxy resin is heated at a moderate temperature of about 160 ° C to 200 ° C for 1 〇 sec to several hours. hardening. Therefore, it is preferable to use a long time (pot fife). The cationic polymerization type catalyst-type curing agent is preferably a photosensitive key salt (for example, an aromatic diazo salt or an aromatic onium salt) which is cured by an energy ray to cure the epoxy resin. Further, in addition to the irradiation of the energy ray, activation by heating causes the epoxy resin to be cured, for example, -18-200946629, such as an aliphatic sulfonium salt. Such a hardener is preferred because it has rapid hardening. When these latent curing is performed using a polyurethane film or a polyester polymer material, a metal film such as nickel or copper, or a coating such as calcium citrate to form a microcapsule, since the usable time can be prolonged, _ 'The radically polymerizable substance contained in the second composition is a substance having a functional group polymerized by a base. Such a radically polymerizable substance Q acrylate (including the corresponding methacrylate, the same applies hereinafter), a propyleneoxy group (containing a corresponding methacryloxy group. The following equivalents, a maleimide compound, a citrate Imine resin, NADIIMIDE resin, etc. The radically polymerizable substance can be used in the state of a monomer. It is also possible to use a monomer and an oligomer. Specific examples of the above propylene compound include methacrylate, ethacrylate, isocyanate, isobutyl acrylate, ethylene glycol diacrylate, didiacrylate, trimethylolpropane triacrylate, Tetrahydroxymethyl hydrazine acrylate, 2-hydroxy-1,3-dipropenyl propylene oxide, 2,2-bis[4-M oxymethoxy)phenyl]propyl, 2,2-bis[4- (Polynoic acid) phenyl] propyl, dicyclopentanyl propyl vinegar, tricyclic guanidine ester, ginseng (propylene oxyethyl) trimeric isocyanate, polyaminomethacrylate, etc. . These can be used individually or in mixture of 2 or more types. Further, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be suitably used. From the viewpoint of improving heat resistance, the acrylate compound preferably has a dicyclopentanyl group, a tricyclic anthracene group, and a triterpenoid ring. At least 1 base of the group. The features of the system are better. By imiding an imine (for example, a compound), or oligomerizing a propyl propylene glycol methane tetra(propylene ethoxy acrylate C, necessary. Further, it is selected from the group -19-200946629 The maleic imine compound has at least two or more maleimine groups in the molecule. The maleimide is, for example, 1-methyl-2,4-bismaleimide benzene, N, N'-meta-phenyl-p-maleimide, N,N'-p-phenylene bismaleimide, anthracene, Ν'-m-toluene bismaleimide, ν,Ν'- 4,4-biphenyl bis-maleimide, :^,1^'-4,4-(3,3'-trimethylbiphenylene) bismaleimide, 1^,> 1'-4,4-(3,3'-dimethyldiphenylmethane) bismaleimide, \,>^'-4,4-(3,3'-diethyldiphenyl Methane) bismaleimide, 11^'-4,4-diphenylmethane bismaleimide, :^chuan '-4,4-diphenylpropane, bismaleimide, anthracene ,Ν'-3,3'-diphenylfluorene, bismaleimide, anthracene, anthracene-4,4-diphenyl ether, bismaleimide, 2,2-bis(4-(4- Maleimide phenoxy)phenyl)propane, 2,2- (3-second butyl-4,8-(4-maleimidophenoxy)phenyl)propane, 1,1-bis(4-(4-maleimide)phenoxy)benzene Base) decane, 4,4'-cyclohexylene-bis(1_(4_maleimide phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-malay) Iminophenoxy)phenyl)hexafluoropropane. These compounds may be used alone or in combination of two or more. The above-mentioned citrate imine resin is one which has at least one citrate imine group in the molecule. The amine compound is produced by polymerization. The citrate imine compound is, for example, phenyl citrate imine, 1-methyl-2,4-bis citrate, hydrazine, hydrazine Sodium citrate, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine (3,3-dimethylbiphenylene) bis citrate, hydrazine, Ν'-4,4-(3,3-dimethyldiphenylmethane) bis citrate, hydrazine, Ν'-4,4-(3,3-Diethyldiphenylmethane) bis citrate, hydrazine, Ν'-4,4-diphenylmethane bis citrate, 200946629]^ ,>1'-4,4-diphenylpropane double citrate Amine, :^,:^'-4,4-diphenyl ether bis citrate, N,N'-4,4-diphenyl maple bis citrate, 2,2-bis (4 - (4-Carbohydrazide phenoxy)phenyl)propane, 2,2_bis(3-secondbutyl-3,4-(4-carbolineimine phenoxy)phenyl Propane, hydrazine, 1-bis(4-(4-carboline quinone) phenoxy) phenyl) decane, 4,4,-cyclohexylene-double' (1-(4- 柠檬康醯亚Amine phenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis-(4-(4- citraconeimimine phenoxy)phenyl)hexafluoropropane. These compounds may be used alone or in combination of two or more. The above nadicimine resin is obtained by polymerizing a dinadiimide compound having at least one dinamidimide group in the molecule. The nadimide compound is, for example, a phenyl nadiimide, a 1-methyl-2,4-di-n-diimide benzene, an N,N'-meta-phenyl-di-n-diimine, an anthracene. ,Ν'-p-phenylene dipyridinium imine, anthracene, anthracene-4,4-biphenylene double nadirimine, N,N'-4,4-(3,3-dimethyl Benzene phenylene) bis-n-diimine, N,N'-4,4-(3,3-dimethyldiphenylmethane) double nadirimine, N,N'-4,4- (3,3-diethyldiphenyl φ methane) bis nadinoimine ' Ν, Ν '-4,4-diphenylmethane bis dinamidimine, hydrazine, Ν '-4,4- Diphenylpropane double nadirimine, anthracene, Ν'-4,4-diphenyl ether double nadirimine, anthracene, Ν'-4,4-diphenyl maple double nadirimine, 2,2-bis(4-(4-nardimidophenoxy)phenyl)propane, 2,2-bis(3-secondbutyl-3,4-(4-nadidecimide) Phenoxy)phenyl)propane, 1,1-bis(4-(4-nardimidophenoxy)phenyl)decane, 4,4'-cyclohexylene-bis(1-(4) - Nadiquinone phenoxy)phenyl)-2-cyclohexylbenzene, 2,2-bis(4-(4-naphthyridinium phenoxy)phenyl)hexafluoropropane. These compounds may be used alone or in combination of two or more. Further, the radical polymerizable substance is preferably used in combination with a radical polymerizable substance having a phosphate structure represented by the following chemical formula (I). At this time, since the adhesion strength to the surface of the inorganic material such as metal is improved, it is suitable for the connection of the circuit electrodes 32 and 42 to each other. [Η1] (Η0^ΪΓΡ— ·〇εΗ2εΗ2'〇—C-C—CH2 * * · (!) J η

[In the above formula, n represents an integer of 1 to 3]. The radically polymerizable substance having the above phosphate structure is obtained by reacting phosphoric anhydride with 2-hydroxyethyl (meth) acrylate. Specific examples of the radical polymerizable substance having a phosphate structure include mono(2-methylpropenyloxyethyl) acid phosphate and bis(2-methylpropenyloxyethyl) acid phosphate. These compounds can be used individually or in mixture of 2 or more types.

The amount of the radically polymerizable substance having a phosphate structure represented by the above formula (I) is preferably 0.01 to 50 by mass based on 100 parts by mass of the total of the radically polymerizable material and the film forming material to be blended as needed. More preferably, it is 0.5 to 5 parts by mass. The above radical polymerizable substance can be used in combination with allyl acrylate. In this case, the blending amount of the allyl acrylate is preferably from 10,000 to 10 parts by mass, more preferably from 0.5 to 5, based on 100 parts by mass of the total of the radically polymerizable material and the film-forming material to be blended as needed. Parts by mass. The hardener which generates a free radical by heating in the second composition means a hardener which generates free radicals after being decomposed by heating. Such a hard -22-200946629 chemical agent is, for example, a peroxidic compound, an azo compound or the like. Such a hardener is appropriately selected depending on the connection temperature, the usable time, and the like. From the viewpoint of high reactivity and improved usable time, an organic peroxide having a half-life of 1 hour and a temperature of 40 ° C or more and a half-life of 1 minute of 180 ° C or less is preferable, and a half life of 10 hours is more preferable. The organic peroxide having a temperature of 60 ° C and having a half-life of 1 minute and having a temperature of 170 ° C or less * 〇 0 The amount of the above-mentioned hardener is set to a connection time of 25 seconds or less, for free The total amount of the base polymerizable material and the film-forming material to be blended is preferably 1 to 10 parts by mass, more preferably 4 to 8 parts by mass. Thereby, a sufficient reaction rate can be obtained. The amount of the curing agent to be added is not limited to 100 parts by mass, more preferably 0.05 to 20 parts by mass, even more preferably 0.1 to 10, based on the total of the radically polymerizable material and the film-forming material to be blended as needed. Parts by mass. Specific examples of the hardening agent which generates free radicals by heating in the second composition include, for example, a decyl peroxide, a peroxydicarbonate, a peroxyester ketal, a dialkyl group. Peroxide, hydroperoxide, formyl peroxide, and the like. Further, from the viewpoint of suppressing corrosion of the circuit electrodes 32 and 42, a curing agent containing a chloride ion or an organic acid having a concentration of 5000 ppm or less is preferable, and a curing agent having less organic acid generated after heating and decomposing is more preferable. Specific examples of such a curing agent include a peroxyester, a dialkyl peroxide, a hydroperoxide, a methoxyalkyl peroxide, and the like, and more preferably a curing agent selected from peroxyesters capable of obtaining high reactivity. The above hardeners can be used in appropriate mixing. -23- 200946629 Peroxyesters such as cumene peroxy neodecanoate, u, 3,3· tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl Oxidized neodecanoate, third hexyl peroxy neodecanoate, tert-butyl peroxy phthalate methyl acetate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexyl Acid ester, 2,5-dimethyl-2,5-di(2-ethylhexyl peroxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate , third hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, 1,1_bis ( Third butyl peroxy) cyclohexane, third hexyl isopropyl peroxy monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl Oxidized laurate, 2,5-dimethyl-2,5-di(m-tolylhydrazone peroxy)hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2 Ethylhexyl monocarbonate, third hexyl peroxide benzoate, tert-butyl peroxyacetate, and the like. Dialkyl peroxides are, for example, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (Third butyl peroxy) hexane, tert-butyl cumyl peroxide. ζ) The hydroperoxide is, for example, diisopropylbenzene hydroperoxide or cumene hydroperoxide. Dimercapto peroxides such as isobutyl peroxide, 2,4-dichlorobenzamide peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, laurel醯 peroxide, stearin peroxide, amber 醯 peroxide, benzamidine peroxide toluene, benzamidine peroxide and the like. Peroxydicarbonates are, for example, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4·•t-butylcyclohexyl)peroxy-24-200946629 dicarbonate, two -2-ethoxymethoxy peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, di-C3-methyl-3-methyl Oxybutyl peroxide peroxydicarbonate and the like. The peroxy ketal is, for example, 1,1-bis(trihexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy)cyclohexane, 1,卜 'bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-(third* butylperoxy)cyclododecane, 2,2-dual (first Tributyl peroxy) decane oxime and the like. For mercapto peroxylation, for example, tert-butyltrimethylformamido peroxide, bis(t-butyl)dimethylformamido peroxide, and tert-butyltrivinylformamidine peroxidation , bis(t-butyl)divinylcarbenyl peroxide, ginseng (t-butyl) vinyl methacrylate peroxide, tert-butyl triallyl peroxide, double Tributyl) diallylguanidinyl peroxide, ginseng (t-butyl) allylmethyl decyl peroxide, and the like. φ These curing agents may be used singly or in combination of two or more kinds, or may be used by mixing a decomposition accelerator, an inhibitor, or the like. Further, these curing agents may be coated with a polyurethane material, a polyester polymer material or the like to form a microcapsule. The microencapsulated hardener can be used for a longer period of use, and therefore it is preferable to use a film forming material as needed in the film-like circuit connecting material of the present embodiment. The film-forming material refers to a method of making the film easy to use and imparting mechanical properties that are not easily broken, broken, or adhered when the composition of the film is formed into a film shape by solidifying the liquid material, and -25- 200946629 It can be used as a film in the normal state (normal temperature and normal pressure). The film forming material is, for example, a phenoxy resin, a polyvinyl formal resin, a polystyrene resin, a polyvinyl butyral resin, a polyester resin, a polyamide resin, a xylene resin, a polyurethane resin. Wait. Among them, since it is excellent in adhesiveness, compatibility, heat resistance, and mechanical strength, it is preferred that the phenoxy resin phenoxy resin reacts a bifunctional phenol with an epihalohydrin until it is polymerized, or 2 A resin obtained by addition polymerization of a functional epoxy resin and a bifunctional phenol. The phenoxy resin can be used in a non-reactive solvent at 40 to 120 ° by using a 2-functional phenolic 1 molar and an epihalohydrin 0.985 to 1.015 mol in the presence of a catalyst such as an alkali metal hydroxide. The reaction is carried out at a temperature of C. Further, 'the phenoxy resin is from the viewpoint of mechanical properties or thermal properties of the resin'. The blending equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol is preferably an epoxy group/benzoquinone hydroxyl group=1/0.9~ 1/1.1, in the presence of a catalyst such as an alkali metal compound, an organophosphorus compound or a cyclic amine compound, a guanamine, an ether, a ketone, a lactone or an alcohol having a boiling point of 120 ° C or higher In an organic solvent such as a 'reaction solid content of 50% by mass or less, it is heated to 50 to 200 ° C' to carry out an addition polymerization reaction. The above bifunctional epoxy resin is, for example, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol s type epoxy resin, a biphenyl diglycidyl ether, a methyl group. Substituted biphenyl diglycidyl ether. The bifunctional phenols have two phenolic hydroxyl groups. Examples of the bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol oxime, methyl substituted bisphenol oxime, dihydroxybiphenyl, methyl substituted dihydroxybiphenyl, and the like. Class of bisphenol 200946629. The phenoxy resin can be modified (e.g., epoxy modified) by a radically polymerizable functional group or other reactive compound. The phenoxy resin may be used singly or in combination of two or more. In the film-form circuit connecting material of the present embodiment, a polymer or a copolymer containing at least one of acrylic acid, acrylate, methacrylate and acrylonitrile as a monomer component may be further contained. Here, from the viewpoint of excellent stress relaxation, it is preferred to use a glycidyl acrylate φ ester containing a glycidyl ether group or a copolymer-based acryl rubber containing a glycidyl methacrylate. The weight average molecular weight of these acrylic rubbers is preferably 200,000 or more from the viewpoint of improving the cohesive force of the adhesive. The film-form circuit connecting material of the present embodiment may further contain rubber fine particles, a chelating agent, a softening agent, an accelerator, an aging preventing agent, a coloring agent, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, and a melamine resin. , isocyanates, and the like. The rubber fine particle system has a mean particle diameter of 2 times or less the average particle diameter of the prepared conductive particles 12 ,, and the storage modulus at room temperature (25 ° C) is the conductive particles 1 2 and the adhesive composition at room temperature. The storage modulus below 1/2 can be used. In particular, the rubber particles are made of polyfluorene oxide, acrylic emulsion, SBR (styrene-butadiene copolymer rubber), NBR (acrylonitrile-butadiene copolymer rubber), and polybutadiene rubber particles. It is preferred to use two or more kinds in combination. These rubber fine particles which have been three-dimensionally crosslinked have excellent solvent resistance and are easily dispersed in the adhesive composition. A chelating agent may be included in the circuit connecting material. Thereby, the connection reliability and the like of the electrical characteristics between the circuit electrodes 32 and 42 can be improved. The chelating agent can be used as long as it has a diameter of -27-200946629 which is 1/2 or less of the particle diameter of the conductive particles 12. Further, when the particles having no conductivity are used, the amount of the chelating agent to be used may be 1 part by volume for the adhesive composition, as long as it is equal to or less than the diameter of the particles having no conductivity. 5 to 60 parts by volume. When the amount is more than 60 parts by volume, the effect of improving the connection reliability tends to be saturated, and when it is less than 5 parts by volume, the effect of the addition of the sputum tends to be insufficient. ^ The above coupling agent contains vinyl, propylene, epoxy or isocyanic acid -

The ester group compound is preferred because it can improve the adhesion. U

[Connection structure of circuit components]

Hereinafter, an embodiment of the connection structure of the circuit member of the present invention will be described in detail. As shown in Fig. 1, the connection structure 1 of the circuit member of the present embodiment includes the first circuit member 30 and the second circuit member 40 which face each other. A circuit connecting member 10 that connects these members is provided between the first circuit member 30 and the second circuit member 40. The circuit connecting member 10 is formed by hardening the film-like circuit connecting material of the above embodiment. Q The first circuit member 30 includes a first circuit board 31 and a 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 second circuit electrode 42 formed on the main surface 41a of the second circuit board 41. The first circuit electrode 32 formed on the main surface 31a of the first circuit board 31 and the second circuit electrode 42 formed on the main surface 41a of the second circuit board 41 are opposed to each other. Further, in the circuit boards 31 and 41, the surfaces of the circuit electrodes 32 and 42 are flat. In the present invention, "the surface of the circuit electrode is flat" means that the surface of the electrode -28-200946629 has an unevenness of 20 nm or less. The circuit connecting member 1 is made of an insulating material 11 and conductive particles 12 which are formed by curing the adhesive resin composition. Connection of circuit members The first circuit electrode 32 and the second circuit electrode 42 that are opposed to each other are electrically connected to the conductive particles 12 included in the circuit connecting member 10. In other words, the conductive particles 12 directly contact both the first circuit electrode 32 and the second circuit • the electrode 42. Specifically, the protruding portion 14 formed by the metal layer 22 (outermost 0 layers) of the conductive particles 12 penetrates the insulating material 11 and contacts both the first circuit electrode 32 and the second circuit electrode 42. Since the protrusions 14 are buried in the circuit electrodes 32 and 42, the contact area between the conductive particles 12 and the circuit electrodes 32 and 42 is increased. Thus, the connection resistance between the circuit electrodes 32, 42 can be sufficiently reduced. "The circuit electrodes 32, 42 can be electrically connected well. Therefore, the current between the circuit electrodes 3 2, 4 2 flows smoothly, and the functions of the circuit can be fully utilized. The thickness of the first circuit electrode 32 or the second circuit electrode 42 is preferably 〇 5 〇 nm or more. When the thickness is less than 50 nm, when the protruding portion 14 on the surface side of the conductive particles contained in the circuit connecting material is pressed by the circuit member, the through-circuit electrodes 32, 42' may be in contact with the circuit substrates 31, 41, and the circuit electrodes 32, 42 and The contact area of the conductive particles 12 is reduced, and the connection resistance tends to increase. The material of the circuit electrodes 32 and 42 is, for example, a metal of Au, Ag, Sn, or Pt or an indium-tin oxide (ITO), indium-zinc oxide (Im), Al or Cr, preferably ITO or IZO. When the circuit electrodes 32 and 42 are composed of ITO or IZO, the long-term reliability of the electrical connection and electrical characteristics between the circuit electrodes is improved -29-200946629. Further, the circuit electrodes 32 and 42 may be entirely composed of the above materials, or only the surface of the circuit electrode may be formed of the above materials. The material of the circuit boards 3 1 and 4 1 is not particularly limited, and is usually an organic insulating material, glass or tantalum. Specific examples of the first circuit member 30 and the second circuit member 40 include a semiconductor wafer such as a semiconductor wafer, a resistor wafer, and a capacitor wafer, and a substrate such as a printed circuit board. These circuit components are usually provided with a plurality of circuit electrodes (circuit terminals). Further, a single circuit electrode may be provided on the circuit member. The form of the connection structure 1 of the circuit member is, for example, a connection structure between a 1C wafer and a substrate on which the wafer is mounted, and a configuration in which the circuits are connected to each other. At least one of the first circuit electrode 32 and the second circuit electrode 42 has a surface area of 150,000 00 or less, and the average number of conductive particles between the first circuit electrode 32 and the second circuit electrode 42 is preferably 3 or more. Here, the average number of conductive particles means the average 値 of the number of conductive particles 12 per one of the circuit electrodes. At this time, the connection resistance between the opposing circuit electrodes 32, 42 can be sufficiently reduced. Further, when the number of the average conductive particles is six or more, a more excellent connection resistance can be achieved. This is because the connection resistance between the circuit electrodes 32 and 42 is sufficiently lowered. When the number of average conductive particles between the circuit electrodes 32 and 42 is two or less, the connection resistance becomes too high, and the electronic circuit tends to be unable to operate normally. [Manufacturing Method of Connection Structure of Circuit Member] Next, a method of manufacturing the connection structure 1 of the above-described circuit member will be described. First, the first circuit member 30, the second circuit member 40, and the circuit -30-200946629 are connected. A film-like circuit connecting material is prepared as a circuit connecting material. The thickness of the film-like circuit connecting material is preferably 10 to 50 μm. Next, a film-like circuit connecting material is placed on the first circuit member 30. The second circuit member 40 is placed on the film-like circuit connecting material in a state in which the circuit electrode 32 of the first circuit member 30 is overlapped with the circuit electrode 42 of the second circuit member 40. Thus, the film-like circuit connecting material φ is interposed between the first circuit member 30 and the second circuit member 40. In this case, since the film-like circuit connecting material is in the form of a film and is easy to handle, when the i-th circuit member 30 and the second circuit member 40 are connected, it is possible to easily interpose between the first circuit member 30 and the second. The connection operation of the circuit member 40. Then, in the first circuit member 30 and the second circuit member 40, the film-like circuit connecting material is heated, and the curing process is performed by pressing, and a circuit is formed between the first circuit member 30 and the second circuit member 40. Q Connection member 1 〇. The hardening treatment can be appropriately selected by a general method which is an adhesive composition. In the present embodiment, the outermost layer (metal layer 22) of the conductive particles 12 in the film-like circuit connecting material is made of a metal having a Vickers hardness of 300 Hv or more, and is harder than the Au which constitutes the outermost layer of the conductive particles. . Therefore, in the hardening treatment of the film-like circuit connecting material, the protruding portion 14 protruding from the metal layer 22 of the conductive particles 12 is the outermost layer of the first or second circuit electrodes 32, 42 as compared with the conventional conductive particles ( The surface of the electrode is buried deep, and the contact area of the conductive particles 12 with the circuit electrodes 32, 42 is increased -31 - 200946629. Further, the diameter of the conductive particles 12 is adjusted to optimize the hardness of the conductive particles 12, so that the conductive particles 12 are formed to be moderately flat, and the contact areas of the circuit electrodes 32 and 42 and the conductive particles 12 become large, and the first and second circuits are formed. The connection resistance between the electrodes 3 2, 4 2 becomes small. When the conductive particles 12 and the first and second circuit electrodes 32 and 42 are in contact with each other, the first circuit member 30 and the second circuit are realized when the adhesive composition in the film-like circuit connecting material is cured. The high bonding strength of the member 40 can maintain a state in which the connection resistance between the circuit electrodes 32 and 42 is small for a long period of time. In other words, in the present embodiment, the hardness of the conductive particles 12 is optimized in accordance with the diameter of the conductive particles 12, and a part of the outermost layer composed of a metal having a Vickers hardness of 30 Å or more is protruded to the outside to form a protrusion. Therefore, regardless of the presence or absence of unevenness on the surface of the first or second circuit electrodes 32 and 42, the connection resistance between the opposing circuit electrodes 32 and 42 can be sufficiently reduced, and good electrical connection between the circuit electrodes 32 and 42 can be achieved. The long-term reliability of the electrical characteristics between the circuit electrodes 3 2, 42 is sufficiently improved. Although a preferred embodiment of the film-like circuit connecting material of the present invention has been described above, the present invention is not limited to the above embodiment. For example, in the above embodiment, the connection structure of the circuit member is manufactured using a film-like circuit connecting material, but a non-film-like circuit connecting material may be used. For example, a solution in which a circuit connecting material is dissolved in a solvent is applied to one of the first circuit member 30 or the second circuit member 40, and dried, and the other circuit member is placed on the dried coating material to connect the circuit. The material is interposed between the first and second circuit members 30 and 40. Further, an insulating layer is provided on the connection structure 1 of the circuit member. However, in the circuit member 30 of the 32-200946629, the first circuit layer 32 or the second circuit member 40 may be formed adjacent to the first circuit electrode 32, and The second circuit electrode 42 is adjacent to the second insulating layer. The insulating layer is not particularly limited as long as it is composed of an insulating material, and is usually composed of an organic insulating material, cerium oxide or tantalum nitride. * [Embodiment] ❹ [Examples] (Production of conductive particles) Change the mixing ratio of tetramethylol methane tetraacrylate, divinylbenzene, and styrene monomer, and use benzammonium peroxide as a polymerization initiator. The suspension polymerization was carried out, and classification was carried out to obtain 26 kinds of core bodies having different particle diameters and hardnesses. Each of the obtained core bodies was treated with electroless Ni plating to the conductive particles No. 1 to 26 shown in Table 〗. In the Ni plating treatment, the plating amount, the processing temperature, and the treatment time were appropriately adjusted, and the plating thickness was changed to form a projection portion made of Ni on the surface (outermost layer) of the conductive particles Q Ν〇·1 to 25. The conductive particles No. 26 did not form a protrusion. Further, Au substitution plating was performed on the Ni particles having the protrusions to form an Au layer having a plurality of protrusions composed of Au, thereby obtaining conductive particles N 〇 . Further, in the same manner as in the case of the conductive particles No. 1 to 26, the surface of the conductive particles obtained by mineralizing Ni on the core body was subjected to substitution plating of Au at a thickness of 25 nm to obtain a uniform thickness, and the most composed of Au. Conductive particle No. 28 of the outer layer. -33- 200946629 The hardness of the conductive particles is a load P (unit: MPa or Kgf) when the conductive particles are deformed by 10% from the diameter of the conductive particles using a micro compression tester (manufactured by Shimadzu Corporation). radius! · (Unit: mm), and the displacement A (unit: mm) at the time of compression is obtained by the following formula 1. Hardness of conductive particles = 3χ2(-1/2) χΡχΔ(·3/2) xr(_1/2) (Formula 1) - ❹ Also, the plurality of conductive particles No.1 are placed on the sticker. On the sample stage with carbon double-sided tape, an electron microscope (S-8〇〇, manufactured by 曰立制制制) was used to adjust the magnification of the electron microscope so that there were more than 10 conductive particles in the field of view, and conductive particles were measured. The particle size of No. 1, the height of the protrusions, and the distance between adjacent protrusions. The particle size is the average enthalpy of the diameter of any of the 10 conductive particles selected. The height of the protrusions and the distance between the adjacent protrusions were measured at five points for the height of the protrusions and the distance between the protrusions of the three selected conductive particles, and the average 値 Q of the obtained 15 data was obtained. Further, the particle diameters of the conductive particles No. 2 to 28, the height of the protrusions, and the distance between the adjacent protrusions were measured in the same manner as in the conductive particle No. 1. -34- 200946629 [Table 1] Conductive particles No. The diameter of the outermost metal protrusions with or without conductive particles (/m) The height of the face (mn) The distance between the protrusions (ran) mst (kgf/mm2) 1 Ni has 1.2 110 510 1200 2 Ni has 1.1 100 500 525 3 Nj has 1,4 90 490 1950 4 Ni has 1.3 120 480 450 5 Ni has 1.7 110 520 2200 6 Ni has 2.6 100 510 1000 7 Ni has 2.5 100 500 500 8 Ni has 2.6 90 500 1680 9 Ni has 2.2 100 510 400 10 Ni has 2.4 110 510 1800 11 Ni has 3.3 90 m 900 12 Ni has 3.2 100 500 430 13 Ni has 3 · 5 110 480 1370 14 Ni has 3.6 100 500 350 15 Ni with 3.7 110 510 1500 16 Ni with 4.4 100 520 800 17 Ni with 4.5 100 500 320 18 Ni with 4.4 100 500 1260 19 Ni with 4.6 90 500 250 20 Ni with 4.7 100 510 1400 21 Ni with 6.2 110 500 850 22 Ni has 6.0 90 490 210 23 Ni has 6.3 100 500 1150 24 Ni has 5.8 90 480 150 25 Ni has 6.4 110 500 1300 26 Ni no 5.6 - - & 50 27 Au has 6.0 110 510 880 28 Au no 5.9 - - 860

(Production of circuit connecting material 1) A phenoxy resin is synthesized from a bisphenol A type epoxy resin and a phenol compound having an anthracene ring structure in the molecule (4,4'-(9-linonic)-diphenyl ether). This resin was dissolved in a mixed solvent having a mass ratio of toluene/ethyl acetate = 50/5, to form a solution having a solid content of 40% by mass. Next, the rubber component is prepared by copolymerization of acrylic rubber (butyl acrylate 40 parts by weight - ethyl acrylate 30 weight - 35 - 200946629 parts - acrylonitrile 30 parts by weight - glycidyl methyl propyl vinegar 3 parts by weight) The weight average molecular weight was 800,000. The acrylic rubber was dissolved in a mixed solvent having a mass ratio of toluene/ethyl acetate = 5 0/5 0 to form a solid content of 15 mass. / 〇 solution. Further prepare a microcapsule-type latent curing agent (microencapsulated amine-based curing agent), bisphenol F-type epoxy resin, and naphthalene-type epoxy resin containing a liquid-like hardener-containing epoxy having a mass ratio of 34:49:17. Resin (epoxy equivalent: 202). The above materials were expressed in terms of solid content, and were prepared by using a phenoxy resin/acrylic rubber/hardener-containing epoxy resin = 2 〇 g / 30 g / 50 g to prepare a composition liquid containing an adhesive. To 100 parts by mass of the composition liquid containing the adhesive, 5 parts by mass of the conductive particles No. 1 were dispersed to prepare a connecting material containing a circuit. The circuit-containing connecting material liquid was applied onto a single-faced, surface-treated polyethylene terephthalate (PET) film having a thickness of 50 μm, and dried by hot air at 70 ° C for 3 minutes in PET. A film-connecting material 1 having a film thickness of 20 μm was obtained on the film. (Production of circuit connecting material 2) 50 g of phenoxy resin (manufactured by Union Carbide Co., Ltd., trade name "PKHC" weight average molecular weight: 5000) was dissolved in toluene/ethyl acetate = 50/50 (mass ratio) In a mixed solvent, a solid content of 40% by mass of a phenoxy resin solution was prepared. 400 parts by mass of polycaprolactone diol having a weight average molecular weight of 80 Å and 131 parts by mass of 2-hydroxypropyl acrylate, the catalyst is 0.5 parts by mass of dibutyl dilaurate, and the polymerization inhibitor is hydroquinone 200946629. 1.0 part by mass of methyl ether was heated to 5 Torr under stirring. (:: The mixture was mixed. Then, 222 parts by mass of isophorone diisocyanate was dropped into the mixed solution, and the temperature was raised to 80 ° C while stirring, and the poly-J-esterification reaction was carried out. The reaction rate of the isocyanate group was confirmed to be 99. After more than %, the reaction temperature is lowered to obtain a polyurethane acrylate. 'Next', the above phenoxy resin solution is weighed to contain a phenoxy resin solution having a solid content of *5 Og, the above-mentioned polyurethane acrylate 49g, and phosphoric acid ester type acrylic acid. The ester lg and a hardener which generates a free radical by heating: 5 g of the third hexylperoxy-2-ethylhexanoate is mixed to obtain a composition liquid containing an adhesive. For the composition liquid 100 containing the adhesive In the mass portion, 5 parts by mass of the conductive particles No. 1 was dispersed to prepare a liquid of the connecting material containing the circuit. Then, the liquid containing the connecting material of the circuit was applied to the one surface by a coating device to a thickness of 50 μm after the surface treatment. On the PET film, after drying at 70 ° C for 3 minutes, a circuit connecting material 2 having a thickness of 20 μm was obtained on the PET film. ❷ (Production of circuit connecting materials 3 to 29) The conductive particles No. 2 to 28 were obtained by substituting the conductive particles No. 1 of the above-mentioned circuit connecting material 1 in the same manner as the circuit connecting material 1 to obtain film-shaped circuit connecting materials 3 to 29, respectively. (Example 1) Preparation A flexible circuit board having a two-layer structure consisting of a polyimide film (thickness: 38 μm) and a Cu foil (thickness: 8 μm) coated with Sn (tin) (37-200946629 (hereinafter referred to as "FPC") as The first circuit member has a circuit line width of 18 μm and a pitch of 50 μm. The glass substrate (thickness: 1.1 mm) having a ΙΤΟ circuit electrode (electrode film thickness, surface resistance < 20 Ω) is prepared as a surface. The second circuit member has a circuit line width of 25 μm and a pitch of 50 μm, and a circuit connecting material 1 cut to a predetermined size (1.5×30 mm) is attached to the second circuit member at 70 ° C. 〇Mpa is heated and pressurized for 5 seconds, and then temporarily connected. Then, after peeling off the PET film, the FPC and the second circuit member are sandwiched between the circuit connecting materials 1 to configure the FPC to perform the FPC circuit and Circuit of the second circuit component Position alignment. Next, with the conditions of 1801, 3\1?, and 15 seconds, the heating and pressurization of the upper part of the FPC and the second circuit member are performed. (Example 2) The same FPC as in the first embodiment was prepared as the first circuit member. Next, an IZO circuit electrode was prepared on the surface (electrode film thickness: 50 am, surface resistance < A glass substrate (thickness: 1.1 mm) of 20 Ω) was used as the second circuit member. The circuit of the second circuit member has a line width of 2 5 μm and a pitch of 50 μm. Then, in the same manner as the connection method of the first embodiment, the circuit connecting material 1 was temporarily connected and formally connected, and the connection structure of the circuit member of the second embodiment was obtained. -38-200946629 (Example 3) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode X electrode film thickness: 5 Onm as in the first embodiment was prepared as the second circuit member. Next, the circuit connecting material 2 cut to a predetermined size (1.5 x 30 mm) was pasted on the second circuit member, heated at 70 ° C, 1.0 M p a for 3 seconds, and then temporarily connected. Then, after the PET film is peeled off, the FPC is placed in a state where the FPC and the second circuit member sandwich the circuit connecting material 2, and the circuit of the FPC circuit and the circuit of the second circuit member are aligned. Next, heating and pressurization were carried out from above the FPC under conditions of 170 ° C, 3 MPa, and 10 seconds to form a formal connection between the FPC and the second circuit member. Thus, the connection structure of the circuit member of the third embodiment was obtained. (Example 4) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the third embodiment, the connection structure of the circuit member of the fourth embodiment is obtained by temporarily connecting and electrically connecting the circuit connecting material 2. (Example 5) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 50 nm) as in Example 1 was prepared as the second circuit member. Then, the connection structure of the circuit member of the fifth embodiment was obtained by the temporary connection and the normal connection by the circuit connecting material 3 in the same manner as in the connection method of the embodiment 1 - 39 to 200946629. (Example 6) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of the sixth embodiment was obtained by "temporary connection and main connection" by the circuit connecting material 3. (Example 7) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: 5 Onm) as in the first embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connecting material 4 was temporarily connected and connected in a normal manner to obtain the connection structure of the circuit member of the seventh embodiment. (Example 8) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 4 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the eighth embodiment. 200946629 (Example 9) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connecting material 7 was temporarily connected and connected in a normal manner to obtain the connection structure of the circuit member of the ninth embodiment. (Example 1 〇) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZ 〇 circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of the tenth embodiment is obtained by temporarily connecting and electrically connecting the circuit connecting material 7. (Example 1 1) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT circuit electrode (electrode film thickness: 50 nm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connecting material 8 was temporarily connected and connected in a normal manner to obtain the connection structure of the circuit member of the eleventh embodiment. (Example 1 2) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZ0 circuit electrode as in the second embodiment was prepared as -41 - 200946629 as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connecting material 8 is temporarily connected and formally connected to obtain the connection structure of the circuit member of the twelfth embodiment. . (Example 1 3) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the embodiment 1^, the circuit connecting material 9 was temporarily connected and connected in a normal manner to obtain the connection structure of the circuit member of the thirteenth embodiment. (Example 1 4) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of the embodiment ◎ 14 was obtained by the temporary connection and the formal connection by the circuit connecting material 9. (Example 1 5) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: 50 nm) as in the first embodiment was prepared as a second circuit member. Next, in the same manner as the connection method of the first embodiment, the temporary connection of the circuit connection material 12 is made to form a connection, and the connection of the % of the embodiment 1 is obtained. _°-42-200946629 (Embodiment 1 6) Preparation The same FPC as in the first embodiment is used as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Next, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of the example 16 is obtained by the temporary connection and the formal connection by the circuit connecting material 12. ❹ (Example 1 7) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: 5 Onm) as in the first embodiment was prepared as the second circuit member. Then, the same as the connection method of the first embodiment, the circuit connection material 13 was temporarily connected and connected, and the connection structure of the circuit member of the seventeenth embodiment was obtained. Q (Example 1 8) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate provided with the IZ〇 circuit electrode of Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connecting material 13 was temporarily connected and formally connected, and the circuit member of the eighteenth embodiment was obtained. (Embodiment 1 9) The FPC of 楗 is used as the first circuit member.捺荽 In the same manner as in the first embodiment, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in the first embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the embodiment, the circuit connecting material 14 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the nineteenth embodiment. (Example 20) The same FPC as in Example 1 was prepared as the first circuit member. Next, the glass substrate having the IZO circuit electrode similar to that of the second embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 14 was temporarily connected and formally connected, and the connection structure of the circuit member of the twenty-second embodiment was obtained. (Example 2 1) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT Ο circuit electrode (electrode film thickness: 50 ηιη) as in the first embodiment was prepared as a second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connecting material 17 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the twenty-first embodiment. (Example 22) The same FPC as in Example 1 was prepared as the first circuit member. Next, a pitch substrate having the same IZ0 circuit electrode as in the second embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 17 is temporarily connected and formally connected, and the connection structure of the circuit member of the example 22 is obtained. (Example 23) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: 50 nm) as in the first embodiment was prepared as a second circuit member. Next, in the same manner as the connection method of the first embodiment, the circuit connection material 18 was temporarily connected and 0 was officially connected, whereby the connection structure of the circuit member of the twenty-third embodiment was obtained. (Example 2 4) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZ0 circuit electrode as in the second embodiment was prepared as the second circuit member. Then, similarly to the connection method of the second embodiment, the circuit connection material 18 was temporarily connected and formally connected, and the connection structure of the circuit member of the twenty-fourth embodiment was obtained. (Example 2 5) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 19 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the twenty-fifth embodiment. (Embodiment 26) -45- 200946629 pieces. Then, the same FPC as in the first embodiment was prepared as the first circuit 擒, and the glass having the same IZO circuit electrode as in the second embodiment was prepared as the second circuit member. Next, the connection method of the second embodiment is temporarily connected and connected by the circuit connecting material 19, and the connection structure of the circuit member of the example 26. (Example 2 7) The same FPC as in Example 1 was prepared as the first circuit member. A glass substrate having the same ITO circuit electrode (electrode film thickness 〇 5 Onm) as in Example 1 was prepared as a second circuit member. Then, in the same manner as the connection method of the embodiment, the circuit connecting material 22 is temporarily connected and formally connected to obtain the connection structure of the circuit member of the twenty-seventh embodiment. (Example 2 8) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 22 was temporarily connected and formally connected, and the connection structure of the circuit member of the twenty-eighth embodiment was obtained. (Example 2 9) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the embodiment 1 - 46 - 200946629, the circuit connection material 23 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the twenty-ninth embodiment. (Example 30) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 23 was temporarily connected and formally connected, and the connection structure of the circuit member of the thirty-ninth embodiment was obtained. (Example 3 1) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 24 was temporarily connected and φ was officially connected, whereby the connection structure of the circuit member of the eleventh embodiment was obtained. (Example 3 2) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 24 was temporarily connected and formally connected, and the connection structure of the circuit member of the twenty-third embodiment was obtained. -47 - 200946629 (Comparative Example 1) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same electrode electrode (electrode film thickness: 5 Onm) as in the first embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 5 was temporarily connected and connected in a normal manner to obtain the connection structure of the circuit member of Comparative Example 1. (Comparative Example 2) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 5 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 2 was obtained. (Comparative Example 3) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: 5 Onm) as in the first embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 6 was temporarily connected and connected in a normal manner to obtain the connection structure of the circuit member of Comparative Example 3. (Comparative Example 4) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZ0 circuit electrode as in the second embodiment was prepared as -48-200946629 as the second circuit member. Next, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of the comparative example 4 was obtained by temporarily connecting the circuit connection material 6 to the 'formal connection' (Comparative Example 5) - The same FpC as in the first embodiment was prepared as The first circuit component. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: ^ 5 Onm) as in the first embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 10 was temporarily connected and connected, and the connection structure of the circuit member of Comparative Example 5 was obtained. (Comparative Example 6) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 10 was temporarily connected and connected by Φ, and the connection structure of the circuit member of Comparative Example 6 was obtained. (Comparative Example 7) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in Example 1 was prepared as the second circuit member. Then, similarly to the connection method of the first embodiment, the circuit connection material 11 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 7 was obtained. -49-200946629 (Comparative Example 8) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of Comparative Example 8 was obtained by temporarily connecting and electrically connecting the circuit connecting material 11. (Comparative Example 9) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 50 nm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 15 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 9 was obtained.

(Comparative Example 1 〇) Q The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate having the same IZ0 circuit electrode as in the second embodiment was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of Comparative Example 10 was obtained by temporarily connecting and forming the connection by the circuit connecting material 15. (Comparative Example 1 1) The same FPC as in Example 1 was prepared as the first circuit member. Next, from -50 to 200946629, a glass substrate having the same ITO circuit electrode (electrode film thickness: 50 nm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 16 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the comparative example 11. (Comparative Example 1 2) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 16 was temporarily connected and formally connected, and the connection structure of the circuit member of the comparative example 12 was obtained. (Comparative Example 1 3) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: φ 5 Onm ) as in Example 1 was prepared as the second circuit member. Then, similarly to the connection method of the first embodiment, the circuit connection material 20 was temporarily connected and formally connected, and the connection structure of the circuit member of the comparative example 13 was obtained. * (Comparative Example 1 4) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 20 is temporarily connected and connected in a conventional manner to obtain a connection structure of the circuit member of the example 14-200946629. (Comparative Example 1 5) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: 50 nm) as in the first embodiment was prepared as a second circuit member. Then, similarly to the connection method of the first embodiment, the circuit connection material 21 was temporarily connected and formally connected, and the connection structure of the circuit member of the comparative example 15 was obtained. (Comparative Example 1 6) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 21 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 16 was obtained. (Comparative Example 1 7) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT0 circuit electrode (electrode film thickness: 50 nm) as in the first embodiment was prepared as a second circuit member. Then, similarly to the connection method of the first embodiment, the circuit connection material 25 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 17 was obtained. (Comparative Example 1 8) -52-200946629 The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the connection structure of the circuit member of Comparative Example 18 was obtained by temporarily connecting and electrically connecting the circuit connecting material 25. (Comparative Example 1 9) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IT Ο circuit electrode (electrode film thickness: 5 Onm) as in the first embodiment was prepared as the second circuit member. Then, similarly to the connection method of the first embodiment, the circuit connection material 26 was temporarily connected and formally connected, and the connection structure of the circuit member of the comparative example 19 was obtained. (Comparative Example 20) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 26 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 20 was obtained. (Comparative Example 2 1) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 50 nm) as in Example 1 was prepared as a second circuit member. Then, in the same manner as the connection method of the embodiment 1-53-200946629, the connection structure of the circuit member of the comparative example 21 was obtained by temporarily connecting and electrically connecting the circuit connecting material 27. (Comparative Example 22) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 27 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 22 was obtained. (Comparative Example 2 3) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 5 Onm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the first embodiment, the circuit connection material 28 was temporarily connected and formally connected, and the connection structure of the circuit member of the comparative example 23 was obtained. (Comparative Example 2 4) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, in the same manner as the connection method of the second embodiment, the circuit connection material 28 was temporarily connected and formally connected, and the connection structure of the circuit member of the comparative example 24 was obtained. -54-200946629 (Comparative Example 2 5) The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate having the same ITO circuit electrode (electrode film thickness: 50 nm) as in Example 1 was prepared as the second circuit member. Then, in the same manner as the connection method of the example i, the circuit connection material 29 was temporarily connected and formally connected, and the connection structure of the circuit member of the comparative example 25 was obtained. (Comparative Example 2 6) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate having the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Then, similarly to the connection method of the second embodiment, the circuit connection material 29 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 26 was obtained. (Comparative Example 2 7) The same FPC as in Example 1 was prepared as the first circuit member. Next, a glass substrate (thickness: 1.1 mm) having an IZO circuit electrode (electrode film thickness: 25 nm, surface resistance < 40 Ω) 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, in the same manner as the connection method of the first embodiment, the circuit connecting material 1 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 27 was obtained. (Measurement of connection resistance) -55- 200946629 Measure between the circuit electrodes of the FPC of the connection structure of the circuit members of the first to third and second and second circuit members using the universal meter Connect the resistor 値. The connection resistance is measured by the resistance 値 (initial resistance 値) after the connection and the resistance 値 after the high temperature and high humidity bath at 80 ° C and 95% RH for 250 hours (after high temperature and high humidity treatment) value). The connecting resistor 値 is the sum of the average 値 at the resistor 37 between the adjacent circuits and the standard deviation multiplied by .3 times (χ + 3σ ). In addition, the rate of increase in resistance is expressed as a percentage of the increase in resistance 値 from the initial resistance 値 to the high-temperature and high-humidity treatment by the initial resistance, and the following formula (resistance after treatment 初期-initial resistance 値) / initial resistance値X 1 00 is calculated. Table 2 'Table 3 shows the measurement results of the connection resistance 値 and the calculation result of the resistance increase rate. Further, the smaller the connection resistance 値, the better the electrical connection between the opposing circuit electrodes, the smaller the resistance increase rate, and the higher the long-term reliability of the electrical characteristics between the circuit electrodes. ❹ -56- 200946629 [Table 2]

Examples and Comparative Examples Circuit Connection Materials The outermost layer of the gold protrusions has a conductive particle diameter (j£/m). Hardness 2 (kgf/mm2) Electrode of the Dijon component () Nea connection resistance (Ω) Increased resistance Rate (%) After initial treatment Example 1 Ni has 1.2 1200 110 (50//η) 112.3 115.6 2.9 Example 2 iZ0 (50^iR) B0.1 83.3 4.0 Example 3 2 Ni has 1.2 1200 1 TO (50 μ η) 113.6 116,9 2.9 Example 4 )ΖΟ(50^η〇81.8 84.5 3.3 Example 5 3 Ni has 1.4 1950 1ΤΟ(50^'«〇120.5 12S.8 4.4 Example 6 ΙΖ0(50μη) 86.7 90.9 4.8 Example 7 4 Ni has 1.1 525 IT0 (50jwb) 110.7 116.0 4.8 Example 8 ΙΖ〇 (50μπ〇79.5 82.7 4.0 Example 9 7 Ni has 2.9 1000 ΠΟ(ΒΟμη) 115.3 119.6 3.7 Example 10 ΙΖ0(50μη) 82.1 85.3 3.9 Example 11 8 Ni has 2.6 1680 ΕΤ0 (50μη) 120.6 126.3 4.7 Example 12 ΙΖΟ (50μπ〇88.6 92. β 4.7 Example 13 9 Ni has 2.2 400 ΙΤΟ (5〇 ίί 114.0 119.4 4.7 Example 14 Ι 20 (50μκ〇81.6 85.5 4.8 Example 15 1 2 Ni has 3.3 900 ΙΤ〇 (50μπ〇116.8 119.6 2.4 Example 16 ΙΖ0(50μη) 83.6 86.7 3.7 Example 17 13 Ni has 3.5 1370 ΙΤ0 (50μη) 121.3 126.7 4.5 Example 18 ΙΖΟ(50μη〇89.2 93,4 4.7 Example 19 14 Ni has 3.6 350 ΙΤΟ(50" «〇115.7 121. ϊ 4.7 Example 20 ΙΖ0(50//η) 82.7 86.7 4.8 Example 21 17 Ni has 4.4 800 ΙΤΟ (50//π〇118.3 122·6 3.6 Example 22 ΙΖ0(50μη) 85.1 88.3 3 , 8 Example 23 18 Ni has 4.4 1260 ITO (50tfn〇122.5 U8.3 4.7 Example 24 IZ0 (5〇iuin) 90.4 94.8 4.9 Example 25 1 9 Ni has 4.6 250 ITD (50//b〇116.2 121.7 4.7 Example 26 IZ0 (50jc/m) 84.3 88.4 4.9 Example 27 22 Ni has 6.2 850 ITO (50^b〇121.3 124.6 2.7 Example 28 IZOCSOmid) 86.3 69.5 3.7 Example 29 23 Ni has 6.3 U50 IT0 (50|im 127.6 133.3 4.5 Example 30 IZO {ΒΟμηΟ 90.4 94.7 4.8 Example 31 24 Ni 5.8 150 ΐΤ0 (50μπ0 119.9 125.6 4.8 Example 32 IZ0(50"m) 84.2 88.3 4.9 -57- 200946629 [Table 3] Examples and Comparison of the outermost protrusions of the material to the presence or absence of conductive particle diameter (/m) mm2 (kgf/mm 勹2Electrical structure of circuit components (): Nalian heterositic resistance (Ω) The initial increase rate of resistance (%) is 1 ^ 5 Νί for children. 1.3 450 iW (50ffeO 112.6 121.0 7.5 No. 2 1ΖΟ(50μη) 80.7 88.7 9.9 than child 3 6 Ni 1.7 2200 ΙΤ0 ($0μη) 133.9 146.2 9.2 Comparison side 4 IZO (50fiR〇112.3 129.1 15.0 mms 1 0 Νί There are 12 4D0 ITO(SOjun) 116.3 126.1 8.4 than the shed β 120 (50μαύ 82.9 91.3 10.1 Comparison for 7 11 Ni with 2.4 1800 ITO (50fiii〇135.6 151.9 12.0 Na 8 ΙΖΟ (5〇ϋβ〇118.7 136.2 14.7 Comparison for θ 1 5 Ni 3.6 350 ΙΤΟ (50μι〇116.3 129.5 11.3 it« for 10 ΙΖΟ(5Ομ·0 83.2 93.8 12.7 than tt case 11 1 6 Ni has 3,7 1500 ΙΤ0(50^η) 130.3 142.5 9.4 Than the shed 12 I20 (50^a0 112.5 131.2 16.6 than the school case 1 3 20 Ni 4.6 250 Π0(50μιι〇117.3 128.4 9.5 ratio (4)1 4 IZO(5〇ai〇85.8 96.8 12.8 than shed 1 5 2 1 Ni has 4· 7 1400 ΙΤ0(50μη) 134.6 151.6 12.5 ratio β for 1 β ΙΖΟ(50μη) 119.7 137.8 55 .1 5.8 150 ΙΤΟ (50μ«〇121 than 6 cases 1 7 25 Ni 4 133.8 9.3 Comparative Example 1 β ΙΖ0 (50μιη} 87.2 86.2 10.3 than 6 cases 1 β 2 6 Ni has $.4 1300 IT0(50/im) 141.3 159.1 12.6 Comparative Example 2 0 iZO(S〇un〇118.2 136.2 15.2 ratio Calibration 2 1 27 Ni m 5.6 8S0 ΙΤΟ(δΟμη) 134.3 145.3 B.2 Ratio shed 2 2 ΙΖ0ΐ50μη} 90.4 112.3 24.2 Comparison for 2 3 28 Au with 6.0 880 ΙΤ0(50μιη) 124.3 136.6 9.9 Ratio 2 2 ΙΖ0 ( 50μη) 86.1 114.2 32.6 Comparative Example 2 5 29 Au m 5.9 860 ΙΤΟ (50μκ〇136.5 165.2 21.0 shed 2 6 120 (50μιι〇91.2 132.6 45.4 than governmental 2 7 1 Ni has 1.2 1200 ΙΤ0 (25μη) 149.4 1&4.2 23.3 The electric resistance increase rate of Examples 1 and 2 in which the metal (the outermost layer metal) constituting the outermost layer of the conductive particles was Ni and the outermost layer formed the protruding portion was 5% or less, and showed a very good number of enthalpy. Further, in Comparative Examples 21 and 22 in which the outermost layer metal was Ni, but the outermost layer did not form the conductive particles of the protrusions, or the comparative example in which the outermost layer metal was Au-based conductive particles, the resistance increase rate was higher than that including All of the examples 1 and 2, and as shown in Examples 1 to 32, 'matching the diameter of the conductive particles (granules - 58 - 200946629 sub-diameter), when the hardness is set to a certain range, the resistance increase rate is known. Below 5%, it shows very good numbers. In the comparative examples 1, 2, 5, 6, 9, 10, 1 3, 1 4, 1 7 and 18, the hardness of the conductive particles was too low, the resistance increase rate was as high as 10%. This is because the conductive particles are too soft, so when the high-temperature and high-humidity treatment causes the pulsation of the distance between the 'circuit electrodes', the shape of the conductive particles cannot change with the distance between the circuit electrodes, causing the conductive particles and the circuit electrodes to fail to charge. φ is caused by partial contact. Further, in Comparative Examples 3, 4, 7, 8, 11, 12, 15, 16, 19, and 20 in which the hardness of the conductive particles was too high, the initial connection resistance was high, and the resistance increase rate was extremely high at 10% or more. This is because the conductive particles are too hard and the conductive particles are not sufficiently flattened, so that the contact area between the conductive particles and the circuit electrodes becomes small. Further, a comparative example of a circuit member comprising a circuit member comprising a circuit electrode having a thickness of 50 nm and a circuit member having a thickness of 25 nm connected to the circuit electrode by a circuit connecting material φ 1 At 2 7 o'clock, the resistance increase rate of Comparative Example 2 7 was around 20%, while the resistance increase rate of Example 1 was small, less than 5%. From this, it is understood that the combination of the circuit connecting material having the conductive particles corresponding to the hardness of the predetermined diameter and the circuit electrode composed of ITO or IZO is formed in the outermost layer made of Ni, and the suppression of the increase rate of the suppression resistance is known. The effect (improvement effect of connection reliability) is remarkable when the thickness of the circuit electrode is 50 nm or more. -59- 200946629 [Industrial Applicability] As described above, according to the present invention, it is possible to provide a good electrical connection between the opposing circuit electrodes even when the surface of the circuit electrode is flat, and at the same time, the circuit can be sufficiently improved. A connection structure of a circuit connecting material and a circuit member for long-term reliability of electrical characteristics between electrodes. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing one embodiment of a connection structure of a circuit member according to the present invention. Fig. 2 (a) and Fig. 2 (b) are schematic cross-sectional views showing conductive particles of a preferred embodiment of the circuit connecting material of the present invention. [Description of main component symbols] 1 : Connection structure of circuit components I 〇 : Circuit connection member II : Insulating material ◎ 12 : Conductive particles 1 4 : Protrusion 2 1 : Nuclei 2 1 a : Intermediate core portion 2 1 b : Core side protrusion portion 22: outermost layer (metal layer) 3 〇: first circuit member 31: first circuit board - 60 - 200946629 3 1 a : main surface 32: first circuit electrode 40 L second circuit member 4 1 : Second circuit board 4 1 a : main surface ' 4 2 : second circuit electrode Η : height of protrusion of conductive particles ❿ s : distance between adjacent protrusions -61 -

Claims (1)

200946629 X. Patent Application No. 1. A circuit connecting material between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode facing the second circuit member. And a circuit connecting material that electrically connects the first circuit electrode and the second circuit electrode, and is characterized in that the adhesive composition and the conductive particles having a diameter of 0.5 to 7 μm are formed, and the outermost layer of the conductive particles is Vickers hardness. (Vickers Hardness) is composed of a metal of 300 Hv or more, and one of the outermost layers protrudes outside, and a protrusion is formed. When the diameter of the conductive particles is 5 μm or more and 7 μm or less, the hardness of the conductive particles is 200 to 1. 200kgf/mm2, the diameter of the conductive particles is 4 μm or more, and when the thickness of the conductive particles is less than 5 μm, the hardness of the conductive particles is 300 to 1 300 kgf/mm 2 , and the diameter of the conductive particles is 3 μm or more, and when the thickness is less than 4 μm, the foregoing The hardness of the conductive particles is 400 to 1 400 kgf/mm 2 , and the diameter of the conductive particles is 2 μm or more, and when the diameter is less than 3 μm, the former The hardness of the conductive particles 450~1 700kgf / mm2, the diameter of the conductive particles are more square · 5 μιη, and less than 2μιη, the hardness of the conductive particles is 5 00~2000kgf / mm2. 2. The circuit connecting material of claim 1, wherein the height of the starting portion is 50 to 500 nm, and one of the outermost layers protrudes from the outer side to form a plurality of the protrusions, and the adjacent protrusions are adjacent to each other. The distance is 1 〇〇〇 nm or less. 3. For the circuit connecting material of claim 1 or 2, _ towel 200946629 The outermost layer is composed of Ni. 4. The circuit connecting material of any one of claims 1 to 3, which is a film 4 dog. 5 1—* 〇. The connection structure of the members is characterized in that the circuit connecting material of any one of the first to fourth items of the invention is interposed between the first circuit member and the aforementioned path member, so that the foregoing The first circuit electrode is electrically connected to the second circuit electrode. A connection structure of a circuit member according to item 5 of the patent application scope, wherein the first or second tracking electrode is an indium-tin oxide. 7. The connection structure of a circuit member according to item 5 of the patent specification of claim 7, wherein the first or the first circuit electrode is indium-zinc oxide. The connection structure of the circuit member according to any one of claims 5 to 7, wherein the thickness of the +^1st or 2nd circuit electrode is 50 nm or more. 63-