TWI395801B - Circuit connection material and circuit structure of the connection structure - 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 0.5-7µm. 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

Connection structure of circuit connecting material and circuit member

The present invention relates to a connection structure of a circuit connecting material and a circuit member.

The connection between the liquid crystal display and the tape carrier package (TCP), the connection between the flexible printed circuit (FPC) and the TCP, or the connection between the FPC and the printed wiring board. When the circuit members are connected to each other, the adhesive is used. A circuit connecting material in which conductive particles are dispersed (for example, an isotropic conductive adhesive). Further, recently, when a semiconductor germanium wafer is mounted on a substrate, the semiconductor germanium wafer is directly mounted on the substrate in order to connect the circuit members without using wiring, so-called flip chip packaging. 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 1] JP-A-59-120436

[Patent Document 2] JP-A-60-191228

[Patent Document 3] Japanese Patent Publication No. 1-251787

[Patent Document 4] Japanese Patent Publication No. 7-90237

[Patent Document 5] JP-A-2001-189171

[Patent Document 6] JP-A-2005-166438

However, in recent years, as electronic devices have become smaller and thinner, the circuit formed by the circuit members has been increased in density, and the distance between adjacent electrodes or the width of the electrodes 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, and curing the other portion by acid or alkali etching. However, the high-density circuit and the substrate are comprehensive. 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 (circuit electrode surface) of the high-density circuit is expected to have a small unevenness, that is, the electrode surface 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 if this method is used, the effect of ensuring long-term reliability of electrical connection and electrical characteristics between circuit electrodes is small due to the specifications (materials, etc.) of the circuit electrodes.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a good electrical connection between opposite circuit electrodes even when the surface of the circuit electrode is flat, and at the same time, the electrical characteristics between the circuit electrodes can be sufficiently improved. Long-term reliability of the circuit connection material and the connection structure of the circuit components.

In order to solve the above problems, the inventors of the present invention have found that the conventional circuit connecting material cannot sufficiently ensure the electrical connection between the circuit electrodes and the long-term reliability of the electrical characteristics, which is the material of the outermost layer of the conductive particles. 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 agent, the protrusion of Au is also deformed so as to be incorporated into 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 diameter of the conductive particles to optimize the hardness of the conductive particles, can improve the long-term reliability of electrical connection and electrical characteristics between circuit electrodes. Sexuality, the present invention has been completed.

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 Hv 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 to 1200 kgf/mm ² , and the diameter of the conductive particles is 4 μm or more. When the thickness is 5 μm, the hardness of the conductive particles is 300 to 1300 kgf/mm ² , 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 1400 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 1700 kgf/mm ² , the diameter of the conductive particles is 0.5 μm or more, and when it is less than 2 μm, the hardness of the conductive particles is 500 to 2000 kgf/mm 2 .

The hardness range of the conductive particles of the present invention is defined by the above unit, and is converted to the current mainstream SI unit, 200 to 1200 kgf/mm ² is 1.961 to 11.768 GPa, and 300 to 1300 kgf/mm ² is 2.942 to 12.749 GPa. The value of 400 to 1400 kgf/mm ² is a value of 3.923 to 13.729 GPa, 450 to 1700 kgf/mm ² is a value of 4.413 to 16.671 GPa, and 500 to 2000 kgf/mm ² is a value of 4.903 to 19.613 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 from the outside to form a protrusion. Therefore, 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. The formation of "flat" conductive particles controls the surface of the circuit electrode, and the direction of the vertical direction is not formed, but is skewed in a direction slightly parallel.

In the above circuit connecting material of the present invention, the height of the protruding portion is 50 to 500 nm, and one of the outermost layers is protruded outward, and a plurality of the protruding portions are formed, and the distance between the adjacent protruding portions is preferably 1000 nm or less.

When the height of the protrusion is less than 50 nm, the connection resistance 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 value tends to be high. When the height is larger than 500 nm, the conductive particles and the conductive particles are Since the contact area between the first and second circuit electrodes is small, the connection resistance value tends to be high.

In the above circuit connecting material of the present invention, the outermost layer is preferably made of Ni.

The effect of the present invention is easily obtained by forming the outermost layer with a metal Ni having a Vickers hardness of 300 Hv 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 according to 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.

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 50 nm, when the circuit members are pressed against each other, the protrusions on the surface of the conductive particles contained in the circuit connecting material penetrate the first or second circuit electrode and may come into contact with 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.

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 electrical characteristics between the circuit electrodes can be sufficiently improved for a long period of time. Sex.

[Best Mode for Carrying Out the Invention]

Preferred embodiments of the present invention will be described in detail below 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 connecting material]

The circuit connecting material of the present invention contains the adhesive composition and the 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, the circuit connecting material can be applied to a support (PET (polyethylene terephthalate) film or the like) using a coating device. It is produced by hot air drying at a predetermined time.

The film-like circuit connecting material contains the conductive particles 12 and the adhesive composition, and the adhesive composition has adhesiveness and is cured 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 first circuit member 30 and the second circuit electrode 42 of the second circuit member 40 are provided. 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 40 can be easily formed. Connection operation.

(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 (metal layer 22) It is configured to facilitate the formation of protrusions by the conductive particles. The core body 21 is composed of a core portion 21a and a core side protrusion portion 21b formed on the surface of the core portion 21a. 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. One of the metal layers 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 300 Hv 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 means the particle diameter of the entire conductive particles 12 having the protrusions 14, which can be measured by electron microscopic observation.

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 1200 kgf/mm ² (1.961 to 11.768 GPa). The diameter of the conductive particles is 4 μm or more, and when it is less than 5 μm, the hardness of the conductive particles is 300 to 1300 kgf/mm ² (2.942 to 12.749 GPa). The diameter of the conductive particles is 3 μm or more, and when it is less than 4 μm, the hardness of the conductive particles is 400 to 1400 kgf/mm ² (3.923 to 13.729 GPa). 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 it is less than 2 μm, the hardness of the conductive particles is 500 to 2000 kgf/mm ² (4.903 to 19.613 GPa).

In the present embodiment, the diameter of the conductive particles 12 is matched, and the hardness of the conductive particles 12 is optimized as described above, and one of the outermost layers of the metal having a Vickers hardness of 300 Hv or more protrudes from the outside to form a protrusion. The electrical connection between the opposing circuit electrodes 32, 42 can be achieved, and the long-term reliability of the electrical characteristics between the circuit electrodes 32, 42 can be sufficiently improved. The relationship between the diameter and hardness of the conductive particles 12 and the electrical connection between the protruding portions and the circuit electrodes 32 and 42 and the long-term reliability of the electrical characteristics will be described below.

When the circuit connecting material is electrically connected between the opposing circuit electrodes 32 and 42, the connection resistance is determined by the number of conductive particles 12 existing between the circuit electrodes 32 and 42 and the contact area between the circuit electrode and each of the conductive particles 12. The contact area changes due to the flatness of the conductive particles 12. In other words, the greater the number of conductive particles 12 existing between the circuit electrodes 32, 42, the lower the connection resistance, and the larger the flatness ratio of the conductive particles 12, the larger the contact area between the circuit electrodes 32, 42 and the conductive particles 12, and the connection The lower the resistance.

The greater the number of conductive particles 12 contained per unit volume of the circuit connecting material, the greater the number of conductive particles 12 present between the circuit electrodes 32, 42. The smaller the diameter of the conductive particles 12, the more the number of conductive particles 12 contained in the unit volume of the circuit connecting material. In contact with the circuit electrodes 32, 42, the number of conductive particles 12 that contribute to the electrical connection between the circuit electrodes 32, 42 is limited by the area of the circuit electrodes 32, 42, so that the circuit electrodes 32, 42 and the respective conductive particles 12 The narrower the contact area, the more. The contact area between the circuit electrodes 32, 42 and the conductive particles 12 is narrower as the flatness ratio of the conductive particles 13 is smaller. The flatness ratio of the conductive particles 12 depends on the hardness of the conductive particles 12, and the smaller the hardness of the conductive particles 12, the smaller.

As described above, when the diameter of the conductive particles 12 is small, the hardness of the conductive particles 12 tends to increase, and the connection resistance between the circuit members 30 and 40 tends to decrease.

On the other hand, when the diameter of the conductive particles 12 is large, the number of the conductive particles 12 existing between the circuit electrodes 32 and 42 is reduced. Therefore, in order to reduce the connection resistance between the circuit members 30 and 40, the circuit electrodes 32 and 42 must be enlarged. The contact area of each of the conductive particles 12. 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 of the hardness corresponding to the diameter of each of the conductive particles, 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 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 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 formed of Au, the protruding portion 14 protruding from the metal layer 22 is easier to handle than the conventional one. In the circuit electrodes 32 and 42, the contact area between the conductive particles 12 and the circuit electrodes 32 and 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.

The organic polymer compound constituting the core portion 21a of the core body 21 may be, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyl resin, a polybutadiene resin or a copolymer thereof. These are cross-linked. The average particle diameter of the core portion 21a in the core body 21 is preferably 0.5 or more and 7 μm 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 resin, a polyoxyl resin, a polybutadiene resin or a copolymer thereof. These cross-linkers can be used. The organic polymer compound constituting the core side protrusion portion 21b may be the same as or different from the organic polymer compound constituting the core portion 21a. The average particle diameter of the core-side protrusions 21b is preferably 50 to 500 nm.

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 strain of a benzoguanamine or the like has a rigid structure and a short distance between cross-linking points. Therefore, the higher the proportion of benzoguanamine or the like which is formed in the whole molecule of the core 21, the harder it is. The conductive particles 12, in addition, increase the degree of crosslinking of the core body 21 of the conductive particles 12, and the hard conductive particles 12 can be obtained. Since acrylate, diallyl phthalate or the like is often changed in distance between crosslinking points, the ratio of acrylate or diallyl phthalate which is formed in the entire molecule of the core body 21 is large. The higher the conductivity, the softer the conductive particles 12 are obtained, and the lower the degree of crosslinking, the soft conductive particles 12 can be obtained.

The metal layer 22 is made of a metal having a Vickers hardness of 300 Hv 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 300 Hv 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 and 42 is easily lowered. When the thickness of the metal layer 22 is less than 50 nm, plating defects and the like are caused, and the connection resistance tends to be large. When the thickness exceeds 170 nm, condensation occurs between the conductive particles, and a short circuit tends to occur between adjacent circuit electrodes. Moreover, the thickness of the metal layer 22 refers to the average thickness of the metal layer 22 from which the protrusions 14 are removed.

The height H 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 value tends to be 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 is small, so that the connection resistance value becomes high. Propensity.

The distance S between the adjacent protrusions 14 is preferably 1000 nm or less, more preferably 500 nm 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 H 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, the magnification of the electron microscope is adjusted so that there are 10 or more, less than 50 conductive particles in the field of view, and the height of the protrusion and the distance between the adjacent protrusions are determined for each of the three selected conductive particles. At 5 o'clock, the average of the 15 data obtained was obtained.

The amount of the conductive particles 12 of the film-like circuit connecting material is preferably 0.1 to 30 parts by volume for 100 parts by volume of 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-circuiting of the circuit electrodes 32 and 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 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"), and a radical-containing substance and A composition of a curing agent that generates free radicals (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, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a novolak epoxy resin, and a cresol novolac 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, ethyl epoxide type epoxy Resin, trimeric isocyanate type epoxy resin, aliphatic chain epoxy resin. These epoxy resins can be halogenated or hydrogenated. These epoxy resins may 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 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 curing agent, the epoxy resin is cured by heating at an intermediate temperature of about 160 ° C to 200 ° C for 10 seconds to several hours. Therefore, the pot fife is longer, so it is preferable. The cationic polymerization type catalyst type curing agent is preferably a photosensitive cerium salt which hardens an epoxy resin by energy ray irradiation (mainly an aromatic diazonium salt or an aromatic sulfonium salt can be used). Further, in addition to the irradiation of the energy ray, the epoxy resin is cured by activation by heating, for example, an aliphatic sulfonium salt or the like. Such a hardener is preferred because of its rapid hardening characteristics.

These latent curings are coated with a polymer material such as a polyurethane or a polyester, or a metal film such as nickel or copper, or an inorganic material such as calcium citrate to form a microcapsule. Time is better.

The radically polymerizable substance contained in the second composition is a substance having a functional group by radical polymerization. Examples of such a radical polymerizable substance include an acrylate (containing the corresponding methacrylate, the same applies hereinafter) compound, a propyleneoxy group (containing the corresponding methacryloxy group, the same applies hereinafter), a maleimide compound, and Nitrate, imidium imine resin, NADIIMIDE resin, etc. The radical polymerizable substance can be used in the form of a monomer or an oligomer, and a monomer and an oligomer can also be used in combination. Specific examples of the above acrylate compound are methacrylate, ethacrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, and trimethylolpropane. Triacrylate, tetramethylol methane tetraacrylate, 2-hydroxy-1,3-dipropenyloxypropane, 2,2-bis[4-(acrylomethoxymethoxy)phenyl]propane, 2, 2-bis[4-(acryloxypolyethoxy)phenyl]propane, dicyclopentenyl acrylate, tricyclodecenyl acrylate, propylene (propylene oxyethyl) trimeric isocyanate, polyamine Carbamate acrylate and the like. These can be used individually or in mixture of 2 or more types. Further, if necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone can be suitably used. In addition, from the viewpoint of improving heat resistance, the acrylate compound preferably has at least one substituent selected from the group consisting of a dicyclopentenyl group, a tricyclodecenyl group, and a triazine ring.

The above maleated imine compound has at least two or more maleimine groups in the molecule. Such maleimides are, for example, 1-methyl-2,4-bismaleimide benzene, N,N'-meta-phenyl-p-maleimide, N,N'-p-phenylene Bismaleimide, N, N'-m-toluene bismaleimide, N, N'-4,4-biphenyl bismaleimide, N, N'-4,4- (3,3'-trimethylbiphenylene) bismaleimide, N,N'-4,4-(3,3'-dimethyldiphenylmethane) bismaleimide, N,N'-4,4-(3,3'-diethyldiphenylmethane) bismaleimide, N,N'-4,4-diphenylmethane bismaleimide, N,N'-4,4-diphenylpropane, bismaleimide, N,N'-3,3'-diphenylfluorene, bismaleimide, N,N'-4,4- Diphenyl ether bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-secondbutyl-4, 8-(4-maleimidophenoxy)phenyl)propane, 1,1-bis(4-(4-maleimidophenoxy)phenyl)decane, 4,4'- Cyclohexylene-bis(1-(4-maleimidophenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-maleimidophenoxy)phenyl) Hexafluoropropane. These compounds may be used alone or in combination of two or more.

The above-mentioned citrate imine resin is obtained by polymerizing a citraconazole compound having at least one citrate imine group in a molecule. The citrate imine compound is, for example, phenyl citrate imine, 1-methyl-2,4-bis citrate imiline benzene, N,N'-meta-phenyl-bis-citraconin, N , N'-p-phenyl phenyl sulfonium imine, N, N'-4,4-biphenyl bis citrate, N, N'-4, 4-(3,3-dimethyl Biphenyl bismuth bisphosphonium imine, N, N'-4,4-(3,3-dimethyldiphenylmethane) bis citrate, N,N'-4,4-( 3,3-Diethyldiphenylmethane) Sodium citrate, N,N'-4,4-diphenylmethane bis citrate, N,N'-4,4-diphenyl Propane bis quinone quinone, N, N'-4,4-diphenyl ether bis citrate, N, N'-4, 4-diphenyl bis bis quinone, 2, 2-bis(4-(4-carboline quinone) phenoxy)phenyl)propane, 2,2-bis(3-second butyl-3,4-(4- citrate) Phenyl)propane, 1,1-bis(4-(4-carbolineimine phenoxy)phenyl)decane, 4,4'-cyclohexylene-bis(1-(4-L. Resveratide phenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-carboconium iminophenoxy)phenyl)hexafluoropropane. These compounds can be used individually or in mixture of 2 or more types.

The above nadicimine resin is obtained by polymerizing a dinadiimide compound having at least one nadimide 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, N , N'-p-phenylene dipyridinium imine, N,N'-4,4-biphenylenedi-n-diimine, N,N'-4,4-(3,3-dimethyl Benzene phenylene) double nadirimine, N,N'-4,4-(3,3-dimethyldiphenylmethane) double nadirimine, N,N'-4,4- (3,3-diethyldiphenylmethane) double nadirimine, N,N'-4,4-diphenylmethane double nadirimine, N,N'-4,4-di Phenylpropane double nadirimine, N,N'-4,4-diphenyl ether double nadirimine, N,N'-4,4-diphenylfluorene double nadirimine, 2 ,2-bis(4-(4-nadiquinimidophenoxy)phenyl)propane, 2,2-bis(3-secondbutyl-3,4-(4-nadidecimidebenzene) Oxy)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-nadidecimidephenoxy)phenyl)hexafluoropropane. These compounds can be used individually or in mixture of 2 or more types.

Moreover, it is preferable to use the radically polymerizable substance together with a radically 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 increased, it is suitable for the subsequent connection of the circuit electrodes 32 and 42.

[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-methylpropoxy oxyethyl) 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. It is more preferably 0.5 to 5 parts by mass.

The above radical polymerizable substance can be used in combination with allyl acrylate. In this case, the amount of the allyl acrylate is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts 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. .

The curing agent which generates free radicals by heating in the second composition means a curing agent which generates free radicals after being decomposed by heating. Such a curing agent is, for example, a peroxidation compound or an azo compound. Such a curing agent 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 10 hours at a temperature of 40 ° C or higher and a half-life of 1 minute at a temperature of 180 ° C or less is preferable, and a half-life of 10 hours is preferable. An organic peroxide having a temperature of 60 ° C or more and a half-life of 1 minute of 170 ° C or less.

When the bonding time is set to 25 seconds or less, the total amount of the radically polymerizable material and the film forming material to be blended is preferably 2 to 10 parts by mass, more preferably 2 to 10 parts by mass. It is 4 to 8 parts by mass. Thereby, a sufficient reaction rate can be obtained. The blending amount of the curing agent in the case where the bonding time is not limited is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass per 100 parts by mass of the radically polymerizable substance and the film forming material to be blended as needed. Share.

Specific examples of the hardener which generates free radicals by heating in the second composition include, for example, a decyl peroxide, a peroxydicarbonate, a peroxyester ketal, and a dialkyl peroxide. , hydroperoxide, formyl peroxide, and the like. Moreover, from the viewpoint of suppressing corrosion of the circuit electrodes 32 and 42, it is preferable to use a hardener having a chloride ion or an organic acid concentration of 5000 ppm or less, and more preferably a hardener having less organic acid generated after heat decomposition. Specific examples of such a curing agent include a peroxyester, a dialkyl peroxide, a hydroperoxide, a formyl peroxide, and the like, and more preferably a curing agent selected from peroxyesters capable of obtaining high reactivity. The above hardeners can be used as appropriate.

Peroxy esters such as cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxide Phthalate ester, third hexyl peroxy neodecanoate, tert-butylperoxytrimethyl acetate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate , 2,5-Dimethyl-2,5-di(2-ethylhexyl peroxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, Trihexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy isobutyrate, 1,1-bis(t-butyl Oxidation) cyclohexane, third hexylperoxy isopropyl monocarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2, 5-dimethyl-2,5-di(m-tolylthioperoxide)hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate And a third hexyl peroxide benzoate, a third butyl peroxyacetate, or 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.

Examples of the hydroperoxide include diisopropylbenzene hydroperoxide, cumene hydroperoxide, and the like.

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)peroxydicarbonate, di-2-ethoxyl Methoxy peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl peroxide Oxidation) dicarbonate and the like.

The peroxy ketal is, for example, 1,1-bis(trihexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy)cyclohexane, 1, 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane, 2,2-dual (third Butyl peroxide, decane, 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.

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 is preferred because it can extend the usable time.

In the film-form circuit connecting material of the present embodiment, a film forming material may be added as needed. The film forming material means that when the liquid material is solidified and the constituent film is formed into a film shape, the film is easily handled and imparted with mechanical properties which are not easily broken, broken, or adhered, and the like. In the state (normal temperature and normal pressure), the user is in the form of a film. 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, a phenoxy resin is preferred because it is excellent in adhesion, compatibility, heat resistance, and mechanical strength.

The phenoxy resin is a resin obtained by reacting a bifunctional phenol with an epihalohydrin until it is polymerized, or a bifunctional epoxy resin and a bifunctional phenol are subjected to addition polymerization. The phenoxy resin can be used in a non-reactive solvent at a temperature of from 40 to 120 ° C in the presence of a catalyst such as an alkali metal hydroxide in the presence of a catalyst such as an alkali metal hydroxide and a 0.95% to 1.015 mole of an epihalohydrin. The reaction is carried out at a temperature of attained. Further, the phenoxy resin is particularly preferably a ratio of the equivalence ratio of the bifunctional epoxy resin to the bifunctional phenol to the epoxy group/phenolic hydroxyl group = 1/0.9 to 1 from the viewpoint of mechanical properties or thermal properties of the resin. /1.1, in the presence of a catalyst such as an alkali metal compound, an organophosphorus compound or a cyclic amine compound, a guanamine type, an ether type, a ketone type, a lactone type, an alcohol type or the like having a boiling point of 120 ° C or higher In the organic solvent, the reaction solid content is 50% by mass or less, and the mixture is heated to 50 to 200 ° C to obtain an addition polymerization reaction.

The bifunctional epoxy resin may, for example, be a bisphenol A epoxy resin, a bisphenol P epoxy resin, a bisphenol AD epoxy resin, a bisphenol S epoxy resin, a biphenyl diglycidyl ether or 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. Bisphenols. The phenoxy resin can be modified (for example, 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-containing glycidyl acrylate or a glycidyl methacrylate-containing copolymer-based acrylic rubber in combination. 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 filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, a melamine resin, Isocyanates and the like.

The rubber fine particle system is such that the average particle diameter is twice or less the average particle diameter of the prepared conductive particles 12, and the storage modulus at room temperature (25 ° C) is storage of the conductive particles 12 and the adhesive composition at room temperature. Only 1/2 of the modulus 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, which can be used alone or in combination. Two or more types are preferably used. These rubber fine particles which have been three-dimensionally crosslinked are excellent in solvent resistance and are easily dispersed in the adhesive composition.

A filler 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 filler can be used as long as it has a maximum diameter of 1/2 or less of the particle diameter of the conductive particles 12. Further, when particles having no conductivity are used in combination, they can be used as long as they are not more than the diameter of the particles having no conductivity. The amount of the filler to be added is preferably from 5 to 60 parts by volume per 100 parts by volume of the adhesive composition. 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 adding the filler tends to be insufficient.

The coupling agent is preferably a compound containing a vinyl group, a propylene group, an epoxy group or an isocyanate group, and the adhesion can be improved.

[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-form circuit connecting material of the above embodiment.

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 face 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 unevenness of the surface of the circuit electrode is 20 nm or less.

The circuit connecting member 10 is composed of an insulating material 11 and conductive particles 12 which are formed by curing an adhesive resin composition. The connection structure 1 of the circuit member is electrically connected to the conductive particles 12 included in the circuit connecting member 10 in which the first circuit electrode 32 and the second circuit electrode 42 are opposed to each other. In other words, the conductive particles 12 directly contact both the first circuit electrode 32 and the second circuit electrode 42. Specifically, the protruding portion 14 formed by the metal layer 22 (outermost layer) 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. Therefore, the connection resistance between the circuit electrodes 32 and 42 can be sufficiently reduced, and the circuit electrodes 32 and 42 can be electrically connected well. Therefore, the current between the circuit electrodes 32 and 42 flows smoothly, and the function of the circuit can be fully utilized.

The thickness of the first circuit electrode 32 or the second circuit electrode 42 is preferably 50 nm or more. When the thickness is less than 50 nm, the protrusions 14 on the surface side of the conductive particles contained in the circuit connecting material penetrate the circuit electrodes 32 and 42 when the circuit member is pressed, possibly contacting the circuit boards 31 and 41, and the circuit electrodes 32 and 42 are 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 indium-tin oxide (ITO), indium-zinc oxide (IZO), Al or Cr, preferably ITO or IZO. When the circuit electrodes 32 and 42 are composed of ITO or IZO, the effect of improving the electrical connection between the circuit electrodes and the long-term reliability of the electrical characteristics is remarkable. Further, the entire circuit electrodes 32 and 42 may be formed of the above-described materials, or only the surface of the circuit electrode may be formed of the above-described materials.

The material of the circuit boards 31 and 41 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 wafer component 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 configuration in which the connection structure between the IC chip and the substrate on which the wafer is mounted and the connection structure between the circuits.

The surface area of at least one of the first circuit electrode 32 and the second circuit electrode 42 is 15000 μm ² 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 an average value 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 and 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 average number of conductive particles between the circuit electrodes 32 and 42 is two or less, the connection resistance is 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 circuit member will be described. First, the first circuit member 30, the second circuit member 40, and the circuit connecting material are prepared.

A film-like circuit connecting material is prepared as a circuit connecting material. The thickness of the film-like circuit connecting material is preferably from 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. In this manner, the film-like circuit connecting material 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, the first circuit member 30 and the second circuit member 40 can be easily interposed therebetween, and the first circuit member 30 and the second can be easily performed. The connection operation of the circuit member 40.

Then, the first circuit member 30 and the second circuit member 40 are subjected to a curing process in a state where the film-like circuit connecting material is heated, and a circuit is formed between the first circuit member 30 and the second circuit member 40. Connecting member 10. 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 between the conductive particles 12 and the circuit electrodes 32, 42 is increased. Further, by matching the diameter of the conductive particles 12, the hardness of the conductive particles 12 is optimized, so that the conductive particles 12 are formed to be moderately flat, and the contact areas between the circuit electrodes 32 and 42 and the conductive particles 12 become large, and the first and second circuit electrodes are formed. The connection resistance between 32 and 42 is 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 member are realized when the adhesive composition in the film-form circuit connecting material is cured. The bonding strength of 40 is high, and at the same time, the connection resistance between the circuit electrodes 32 and 42 is kept 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 one of the outermost layers of the metal having a Vickers hardness of 300 Hv or more protrudes outside, forming 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 32, 42 is improved.

Although the 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, although the insulating layer is provided on the connection structure 1 of the circuit member, the first circuit layer 30 may be formed adjacent to the first circuit electrode 32 to form the first insulating layer, or the second circuit member 40 may be connected to the second circuit electrode. 42 is adjacent to form a 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.

[Examples]

(Production of conductive particles)

Changing the mixing ratio of tetramethylol methane tetraacrylate, divinylbenzene and styrene monomer, suspending polymerization using benzammonium peroxide as a polymerization initiator, and then classifying to obtain different particle diameters and hardnesses 26 species of nucleus. Each of the obtained core bodies was treated with electroless Ni plating to the conductive particles No. 1 to 26 shown in Table 1. In the Ni plating treatment, the amount of the plating solution, the processing temperature, and the treatment time were appropriately adjusted, and the plating thickness was changed to form a projection made of Ni on the surface (outermost layer) of the conductive particles No. 1 to 25. The conductive particles No. 26 did not form a protrusion.

Further, Au-plated plating was performed on the Ni particles having the protrusions, and an Au layer having a plurality of protrusions made of Au was formed to obtain conductive particles No. 27.

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 plating 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.

The hardness of the conductive particles is a load P (unit: MPa or Kgf) when the conductive particles are deformed by 10% of the diameter of the conductive particles using a micro compression tester (manufactured by Shimadzu Corporation), and the radius r of the conductive particles (unit) :mm), and the displacement Δ (unit: mm) at the time of compression is obtained by the following formula 1.

The hardness of the conductive particles = 3 × 2 ^(-1/2) × P × Δ ^(-3/2) × r ^(-1/2) ‧‧‧ (Formula 1)

In addition, a plurality of conductive particles No. 1 were uniformly placed on a sample stage on which a carbon double-sided tape was attached, and an electron microscope (S-800, manufactured by Hitachi, Ltd.) was used to adjust the magnification of the electron microscope so that there were 10 or more fields of view. The number of conductive particles of less than 50 was measured, and the particle diameter of the conductive particle No. 1, the height of the protrusion, and the distance between the adjacent protrusions were measured. The particle size is the average of the diameters of the arbitrarily selected 10 conductive particles. 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 value of the obtained 15 data was obtained. Further, in the same manner as in the conductive particle No. 1, 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.

(Production of circuit connecting material 1)

A phenoxy resin is synthesized from a bisphenol A type epoxy resin and a phenol compound (4,4'-(9-fluorenylene)-diphenyl ether) having an anthracene ring structure in the molecule, and the resin is dissolved in a mass ratio of In a mixed solvent of toluene/ethyl acetate = 50/50, a solution having a solid content of 40% by mass was formed. Next, the rubber component was prepared as an acrylic rubber (40 parts by weight of butyl acrylate - 30 parts by weight of ethyl acrylate - 30 parts by weight of acrylonitrile - 3 parts by weight of glycidyl methacrylate), and a weight average molecular weight of 800,000. This acrylic rubber was dissolved in a mixed solvent having a mass ratio of toluene/ethyl acetate = 50/50 to form a solution having a solid content of 15% by mass. Further prepare a microcapsule-type latent curing agent (microencapsulated amine-based curing agent), bisphenol P-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 formulated in a ratio of phenoxy resin/acrylic rubber/hardener-containing epoxy resin=20 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, the conductive particles No. 1 was dispersed by 5 parts by mass to prepare a liquid material for connection with a circuit. The circuit-containing connecting material liquid was applied onto a single-faced, 50 μm-thick polyethylene terephthalate (PET) film, and dried by hot air at 70 ° C for 3 minutes in a PET film. A film-like material 1 having a film thickness of 20 μm was obtained.

(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 a mixed solvent of toluene/ethyl acetate = 50/50 (mass ratio) to prepare a solid content. 40% by mass of a phenoxy resin solution. 400 parts by mass of polycaprolactone diol having a weight average molecular weight of 800 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 monomethyl ether. 1.0 part by mass, heated to 50 ° C under stirring to carry out mixing. Then, 222 parts by mass of isophorone diisocyanate was dropped from the mixed solution, and the mixture was heated to 80 ° C while stirring to carry out a polyurethaneization reaction. After confirming that the reaction rate of the isocyanate group was 99% or more, the reaction temperature was lowered to obtain a polyurethane acrylate.

Next, the phenoxy resin solution was weighed to obtain a phenoxy resin solution containing 50 g of a solid component, 49 g of the above-mentioned polyurethane acrylate, 1 g of a phosphate ester acrylate, and a hardener which generates free radicals by heating: a third hexyl group 5 g of peroxy-2-ethylhexanoate was mixed to obtain a composition liquid containing an adhesive. To 100 parts by mass of the composition liquid containing the adhesive, the conductive particles No. 1 was dispersed by 5 parts by mass to prepare a connection material liquid containing a circuit. Then, the connection material liquid containing the circuit was applied onto a PET film having a thickness of 50 μm which was surface-treated on one side, and dried by hot air at 70 ° C for 3 minutes, and then a thickness of 20 μm was obtained on the PET film. Circuit connection material 2.

(Production of circuit connecting materials 3~29)

A film-like circuit connecting material 3 to 29 was obtained in the same manner as the circuit connecting material 1 except that the conductive particles No. 2 to 28 were used instead of the conductive particles No. 1 of the circuit connecting material 1. The characteristics of the conductive particles used in the production of the respective circuit connecting materials are shown in Table 2.

(Example 1)

A flexible circuit board having a two-layer structure composed of a polyimide film (thickness: 38 μm) and a Sn (tin)-plated Cu foil (thickness: 8 μm) was prepared. (hereinafter referred to as "FPC") as the first circuit member. The circuit of this FPC has a line width of 18 μm and a pitch of 50 μm.

A glass substrate (thickness: 1.1 mm) having an ITO circuit electrode (electrode film thickness: 50 nm, surface resistance < 20 Ω) was provided on the surface as a second circuit member. The circuit of the second circuit member has a line width of 25 μm and a pitch of 50 μm.

Next, the circuit connecting material 1 cut into a predetermined size (1.5 × 30 mm) was pasted on the second circuit member, heated at 70 ° C and 1.0 Mpa for 5 seconds, and then temporarily connected. Next, after peeling off the PET film, the FPC and the second circuit member are sandwiched between the circuit connecting materials 1 to arrange the FPC, and the circuit of the FPC circuit and the second circuit member are aligned. Next, heating and pressurization were performed from above the FPC under conditions of 180 ° C, 3 MPa, and 15 seconds to form an official connection between the FPC and the second circuit member. Thus, the connection structure of the circuit member of Example 1 was obtained.

(Example 2)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate (thickness: 1.1 mm) having an IZO circuit electrode (electrode film thickness: 50 nm, surface resistance < 20 Ω) on the surface was prepared as a second circuit member. The circuit of the second circuit member has a line width of 25 μm and a pitch of 50 μm. Then, similarly to the connection method of the first embodiment, the circuit connection material 1 was temporarily connected and formally connected, and the connection structure of the circuit member of the second embodiment was obtained.

(Example 3)

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. Next, the circuit connecting material 2 cut into a predetermined size (1.5 × 30 mm) was pasted on the second circuit member, heated at 70 ° C and 1.0 Mpa for 3 seconds, and then temporarily connected. Next, after peeling off the PET film, the FPC is placed in a state in which the circuit component 2 is sandwiched between the FPC and the second circuit member, and the FPC circuit is placed in alignment with the circuit of the second circuit member. Next, heating and pressurization were performed from above the FPC under the 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 Example 3 was obtained.

(Example 4)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 third embodiment, the circuit connection material 2 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the fourth embodiment.

(Example 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. Next, in the same manner as the connection method of the first embodiment, the circuit connection material 3 was temporarily connected and formally connected, and the connection structure of the circuit member of the fifth embodiment was obtained.

(Example 6)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 3 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the sixth embodiment.

(Example 7)

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 first embodiment, the circuit connection material 4 was temporarily connected and formally connected, and the connection structure of the circuit member of the seventh embodiment was obtained.

(Example 8)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 4 was temporarily connected and formally connected, and the connection structure of the circuit member of the eighth embodiment was obtained.

(Example 9)

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, similarly to the connection method of the first embodiment, the circuit connection material 7 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the ninth embodiment.

(Embodiment 10)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 7 was temporarily connected and formally connected, and the connection structure of the circuit member of the tenth embodiment was obtained.

(Example 11)

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. Next, similarly to the connection method of the first embodiment, the circuit connection material 8 was temporarily connected and formally connected, and the connection structure of the circuit member of the eleventh embodiment was obtained.

(Embodiment 12)

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. It is the second circuit member. Next, similarly to the connection method of the second embodiment, the circuit connection material 8 was temporarily connected and formally connected, and the connection structure of the circuit member of the twelfth embodiment was obtained.

(Example 15)

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 first embodiment, the circuit connection material 12 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the fifteenth embodiment.

(Embodiment 16)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 12 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the sixteenth embodiment.

(Example 17)

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, similarly to the connection method of the first embodiment, the circuit connection material 13 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the seventeenth embodiment.

(Embodiment 18)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 13 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the eighteenth embodiment.

(Example 21)

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 first embodiment, the circuit connection 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 the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 17 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the twenty-second embodiment.

(Example 23)

The same FPC as in the first embodiment was prepared as the first circuit member. then 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 18 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the twenty-third embodiment.

(Example 24)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 circuit connection material 18 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the twenty-fourth embodiment.

(Example 27)

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, similarly to the connection method of the first embodiment, the circuit connection material 22 was temporarily connected and formally connected, and the connection structure of the circuit member of the twenty-seventh embodiment was obtained.

(Embodiment 28)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 22 is temporarily connected and formally connected, and is implemented. The connection structure of the circuit member of Example 28.

(Example 29)

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, similarly to the connection method of the first embodiment, the circuit connection material 23 was temporarily connected and formally connected, and the connection structure of the circuit member of the twenty-ninth embodiment was obtained.

(Embodiment 30)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 23 was temporarily connected and formally connected to obtain the connection structure of the circuit member of the thirty-ninth embodiment.

(Comparative Example 1)

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 first embodiment, the circuit connection material 5 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 1 was obtained.

(Comparative Example 2)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 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 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. Next, similarly to the connection method of the first embodiment, the circuit connection material 6 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 3 was obtained.

(Comparative Example 4)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Next, similarly to the connection method of the second embodiment, the circuit connection material 6 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 4 was obtained.

(Comparative Example 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. Second, with the embodiment 1 In the same manner, the connection structure of the circuit member of Comparative Example 5 was obtained by temporarily connecting and connecting the circuit connecting material 10 in the same manner.

(Comparative Example 6)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 formally connected, and the connection structure of the circuit member of Comparative Example 6 was obtained.

(Comparative Example 7)

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 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.

(Comparative Example 8)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 11 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 8 was obtained.

(Comparative Example 9)

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, similarly to 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 10)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Next, similarly to the connection method of the second embodiment, the circuit connection material 15 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 10 was obtained.

(Comparative Example 11)

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. Next, similarly to the connection method of the first embodiment, the circuit connection material 16 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 11 was obtained.

(Comparative Example 12)

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. It is the second circuit member. Next, 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 13)

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 first embodiment, the circuit connection material 20 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 13 was obtained.

(Comparative Example 14)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including the same IZO circuit electrode as in Example 2 was prepared as the second circuit member. Next, similarly to the connection method of the second embodiment, the circuit connection material 20 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 14 was obtained.

(Comparative Example 15)

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, 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 Comparative Example 15 was obtained.

(Comparative Example 16)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 17)

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, 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 18)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 25 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 18 was obtained.

(Comparative Example 19)

The same FPC as in the first embodiment was prepared as the first circuit member. then 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, 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 Comparative Example 19 was obtained.

(Comparative Example 20)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 21)

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, similarly to the connection method of the first embodiment, the circuit connection material 27 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 21 was obtained.

(Comparative Example 22)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 circuit connection material 27 is temporarily connected and formally connected to obtain a comparison. The connection structure of the circuit member of Example 22.

(Comparative Example 23)

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, similarly to 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 Comparative Example 23 was obtained.

(Comparative Example 24)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 Comparative Example 24 was obtained.

(Comparative Example 25)

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, similarly to the connection method of the first embodiment, the circuit connection material 29 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 25 was obtained.

(Comparative Example 26)

The same FPC as in the first embodiment was prepared as the first circuit member. Next, a glass substrate including 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 29 was temporarily connected and formally connected, and the connection structure of the circuit member of Comparative Example 26 was obtained.

(Comparative Example 27)

The same FPC as in the first embodiment 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 connection 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)

The circuit electrode between the circuit electrode of the FPC and the circuit electrode of the second circuit member of the connection structure of the circuit members of Comparative Examples 1 to 12, 15 to 18, 21 to 24, and 27 to 30 of Examples 1 to 12 was measured using a universal electric meter. Connect the resistance value. The connection resistance value is determined by the resistance value (initial resistance value) immediately after the connection and the resistance value after the high temperature and high humidity bath at 80 ° C and 95% RH for 250 hours (after high temperature and high humidity treatment) (resistance after treatment) ). The connection resistance value is the sum of the average value at the resistance 37 between adjacent circuits and the value by multiplying the standard deviation by 3 times (x + 3σ). Also, the resistance increase rate will be from the initial resistance value to the high The increase in the resistance value after the temperature-high humidity treatment is expressed as a percentage by the value obtained by dividing the initial resistance value, and is calculated by the following formula (resistance after treatment - initial resistance value) / initial resistance value × 100. Table 2 and Table 3 show the measurement results of the connection resistance value and the calculation results of the resistance increase rate. Further, the smaller the connection resistance value is, the better the electrical connection between the opposing circuit electrodes is, and the smaller the resistance increase rate is, the higher the long-term reliability of the electrical characteristics between the circuit electrodes is.

In Examples 1 and 2 in which the metal (the outermost layer metal) constituting the outermost layer of the conductive particles was Ni and the conductive particles of the outermost layer were formed, the resistance increase rate was 5% or less, which showed a very good numerical value. 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 examples 23 to 26 in which the outermost layer metal was the conductive particles of Au, the resistance increase rate was higher than that in the examples. All embodiments of 1, 2.

Moreover, as shown in Embodiments 1 to 12, 15 to 18, 21 to 24, and 27 to 30, When the hardness (particle diameter) of the conductive particles was set and the hardness was set to a certain range, it was found that the resistance increase rate was 5% or less, and a very good value was exhibited.

On the other hand, in Comparative Examples 1, 2, 5, 6, 9, 10, 13, 14, 17, and 18 in which 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. Therefore, when the distance between the opposing circuit electrodes is disturbed by the high-temperature and high-humidity treatment, the shape of the conductive particles cannot be changed in accordance with the distance between the electrodes of the circuit, and the conductive particles are not sufficiently contacted with the circuit electrodes. Caused by it.

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 flat, so that the contact area between the conductive particles and the circuit electrodes is reduced.

Further, in the case of the circuit member in which the circuit connecting material 1 is connected to the circuit member having the circuit electrode of ITO having a thickness of 50 nm, the first embodiment is connected to the comparative example 27 in which the circuit member is a circuit member in which the circuit electrode is made of ITO having a thickness of 25 nm. The resistance increase rate of Comparative Example 27 was about 20% before and after, and the resistance increase rate of Example 1 was small, which was less than 5%. This shows that the protrusion is formed on the outermost layer made of Ni, and 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 suppresses the suppression of the increase rate of the resistance. The effect (improvement effect of connection reliability) is remarkable when the thickness of the circuit electrode is 50 nm or more.

[Industrial use]

As described above, according to the present invention, it is possible to provide a circuit which can achieve a good electrical connection between the opposing circuit electrodes even when the surface of the circuit electrode is flat, and can sufficiently improve the electrical characteristics between the circuit electrodes. Connection structure of connecting material and circuit member.

1‧‧‧ Connection structure of circuit components

10‧‧‧Circuit connection components

11‧‧‧Insulating substances

12‧‧‧Electrical particles

14‧‧‧Protruding

21‧‧‧ nuclear body

21a‧‧‧Nuclear Department

21b‧‧‧Nuclear side protrusion

22‧‧‧ outermost layer (metal layer)

30‧‧‧1st circuit component

31‧‧‧1st circuit substrate

31a‧‧‧Main face

32‧‧‧1st circuit electrode

40‧‧‧2nd circuit component

41‧‧‧2nd circuit substrate

41a‧‧‧Main face

42‧‧‧2nd circuit electrode

H‧‧‧ Height of protrusions of conductive particles

S‧‧‧distance between adjacent protrusions

Fig. 1 is a schematic cross-sectional view showing a preferred 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.

1. . . Connection structure of circuit components

10. . . Circuit connecting member

11. . . Insulating substance

12. . . Conductive particle

14. . . Protrusion

21a. . . Central Nuclear Department

twenty two. . . Outermost layer (metal layer)

30. . . First circuit component

31. . . First circuit substrate

31a. . . Main face

32. . . First circuit electrode

40. . . Second circuit component

41. . . Second circuit substrate

41a. . . Main face

42. . . Second circuit electrode

Claims (8)

A circuit connecting material is interposed between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode facing the first circuit member, and the first circuit electrode and the first circuit electrode are The circuit connecting material for electrically conducting the second circuit electrode is characterized in that it comprises an adhesive composition and conductive particles having a diameter of 0.5 μm or more and less than 4 μm, and the outermost layer of the conductive particles is Vickers Hardness. It is composed of Ni or Ni alloy of 300 Hv or more, and one of the outermost layers protrudes outward, and a protrusion is formed. 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 1400 kgf. /mm ² , the diameter of the conductive particles is 2 μm or more, and when the thickness is less than 3 μm, the hardness of the conductive particles is 450 to 1700 kgf/mm ² , and the diameter of the conductive particles is 0.5 μm or more, and when the thickness is less than 2 μm, the conductive The hardness of the particles is 500 to 2000 kgf/mm ² . The circuit connecting material of claim 1, wherein the protrusion has a height of 50 to 500 nm, and one of the outermost layers protrudes from the outer side to form a plurality of the protrusions, and the distance between the adjacent protrusions is Below 1000nm. The circuit connecting material of claim 1 or 2 is in the form of a film. A connection structure of a circuit member, characterized in that the circuit connecting material according to any one of claims 1 to 3 is interposed between the first circuit member and the second circuit member, and the first circuit electrode and the first circuit electrode are The second circuit electrode is electrically connected, and the thickness of the first and second circuit electrodes is 50 nm or more. The connection structure of the circuit member of claim 4, wherein the first or second circuit electrode is an indium-tin oxide. The connection structure of the circuit member according to the fourth aspect of the invention, wherein the first or second circuit electrode is an indium-zinc oxide. The connection structure of the circuit member of claim 4, wherein only the surface of the first or second circuit electrode is indium-tin oxide. The connection structure of the circuit member of claim 4, wherein only the surface of the first or second circuit electrode is indium-zinc oxide.