JP5757228B2 - Anisotropic conductive adhesive, manufacturing method thereof, connection structure and manufacturing method thereof - Google Patents

Description

  The present invention relates to an anisotropic conductive adhesive in which insulating coated magnetic conductive particles are dispersed in an insulating adhesive.

  An anisotropic conductive adhesive is manufactured by dispersing conductive particles in an insulating adhesive, and is used in a paste or film form. In this case, as the conductive particles, particles that are very small compared to the conventional one having a particle size of about 1 to 5 μm according to the fine pitch of the wiring are used. Resin core nickel plated particles with electroless nickel plated layer formed on the surface of the resin particles as a material that exhibits conductivity and deformability suitable for anisotropic conductive connection and has relatively low cost. Is widely used (Patent Document 1).

  In addition, for anisotropic conductive adhesives, in order to achieve good anisotropic conductive connection, the insulation in the direction orthogonal to the connection direction (anisotropic conductive connection direction) during anisotropic conductive connection is improved. However, as a method for that, providing a coating layer of an insulating resin on the surface of the conductive wire particles has been performed.

JP 2009-259787 A

  However, if the resin core nickel plating particles, which are relatively easily deformed, are used as the conductive particles of the anisotropic conductive adhesive and are further provided with an insulating resin coating layer, the resin core nickel plating with insulation coating is used. The amount of particles penetrating into the surface of the electrode to be anisotropically conductive decreases, and as a result, the non-conductive film becomes difficult to break and may increase the connection resistance value during anisotropic conductive connection. There was no problem.

  An object of the present invention is to solve the above-described problems of the conventional technology, and to make a metal oxide film or the like nonconductive without reducing insulation in a direction orthogonal to the anisotropic conductive connection direction. It is an object of the present invention to provide an anisotropic conductive adhesive containing insulating-coated magnetic conductive particles that can penetrate into the surface of an electrode to be anisotropically conductively connected so as to break through the film and does not increase the connection resistance value.

  In addition to insulating coating magnetic conductive particles having a relatively large particle size, the inventor demagnetized in an insulating adhesive containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. If an anisotropic conductive adhesive is constituted by containing magnetic conductive fine particles having a relatively small particle diameter that has been magnetized after the treatment in a specific amount range, the insulating adhesive flows during anisotropic conductive connection. Along with this, the magnetically conductive magnetic particles are strongly adhered to the surface of the insulating coated magnetic conductive particles by their magnetism to the extent that they do not fall off during anisotropic conductive connection, and the magnetic conductive fine particles have an uneven shape as a whole. I found out that

  Furthermore, the present inventor has orthogonally crossed the anisotropic conductive connection direction by thermocompression bonding in the anisotropic conductive connection using the anisotropic conductive adhesive containing the insulating conductive magnetic conductive particles having such surface irregularities. Magnetic insulation in which the insulation coating of the insulation coated magnetic conductive particles and the non-conductive film on the electrode surface to be anisotropically conductive become the surface protrusions of the insulation coated magnetic conductive particles without reducing the insulation resistance in the direction It has also been found that a good anisotropic conductive connection (low connection resistance value) can be achieved by breaking through with fine particles.

  Based on these findings, the present inventor has completed the following present invention.

  That is, the present invention provides an anisotropic conductive adhesive in which insulating coated magnetic conductive particles are dispersed in an insulating adhesive containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. Insulating coated magnetic conductive particles are demagnetized, and magnetic conductive fine particles magnetized after demagnetization are formed into a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and silane. It is contained in an amount of 5 to 70 parts by mass with respect to a total of 100 parts by mass of the coupling agent, and the magnetic conductive fine particles have an average particle diameter of 0.05 to 0.5 μm, and the average particle diameter is the insulating coating. An anisotropic conductive adhesive characterized by being 1 to 10% of the average particle diameter of magnetic conductive particles is provided.

Moreover, this invention is a manufacturing method of the above-mentioned anisotropic conductive adhesive, Comprising: The following processes (A) and (B):
Process (A)
A step of demagnetizing the insulating coated magnetic conductive particles, and a step of magnetizing the magnetic conductive fine particles after demagnetizing; and step (B)
Insulating coated magnetic conductive particles demagnetized to an insulating adhesive containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent and a silane coupling agent, and magnetic conductive fine particles magnetized after the demagnetization treatment The manufacturing method which has the process of mixing and dispersing is provided.

In the production method of the present invention, when the anisotropic conductive adhesive is a film, the following step (C) follows the step (B):
Process (C)
It is preferable to have the process of forming an anisotropic conductive film by apply | coating an anisotropic conductive adhesive to the single side | surface of a peeling base material, and drying.

  Further, according to the present invention, the terminal of the first electronic component and the terminal of the second electronic component are anisotropically conductively connected by the above-described anisotropic conductive adhesive of the present invention. Provide a structure.

  In addition, the present invention is a method for manufacturing a connection structure in which a terminal of a first electronic component and a terminal of a second electronic component are connected, the terminal of the first electronic component and the second electronic component By placing the anisotropic conductive adhesive of the invention described above between the terminals of the component and pressing the first electronic component against the second electronic component while heating the anisotropic conductive adhesive, the terminal Provided is a method of manufacturing a connection structure characterized by anisotropically connecting each other.

  The anisotropic conductive adhesive of the present invention is different from the insulating conductive magnetic conductive particles dispersed in an insulating adhesive containing a film forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. An isotropic conductive adhesive in which insulating coated magnetic conductive particles are demagnetized, and magnetic conductive fine particles magnetized after demagnetization are formed into film-forming resin, liquid epoxy compound, epoxy 5 to 70 parts by mass with respect to 100 parts by mass in total of the curing agent and the silane coupling agent. In addition, magnetic conductive fine particles having an average particle diameter of 0.05 to 0.5 μm and an average particle diameter of 1 to 10% of the average particle diameter of the insulating coated magnetic conductive particles are used. For this reason, the magnetic conductive fine particles having a relatively small particle diameter magnetized after the demagnetization process adhere to the surface of the insulating coated magnetic conductive particles having a relatively large particle diameter. As a result, the insulating coated magnetic conductive particles behave in the same manner as particles having an uneven shape as a whole. Therefore, the insulation coating of the magnetic coating particles of the insulating coating without reducing the insulation resistance in the direction orthogonal to the direction of the anisotropic conductive connection by thermocompression bonding in the anisotropic conductive connection using the anisotropic conductive adhesive And the non-conductive film on the surface of the electrode to be anisotropically conductive are pierced by the magnetic conductive fine particles that form the convex portions of the surface of the insulation-coated magnetic conductive particles, so that a good anisotropic conductive connection (low connection resistance value) Is possible.

FIG. 1 is a schematic cross-sectional view of the anisotropic conductive adhesive of the present invention formed into a film. FIG. 2 is an explanatory diagram of a demagnetizing device for demagnetizing magnetic conductive fine particles. FIG. 3 is an explanatory diagram of a demagnetizing device for demagnetizing magnetic conductive fine particles.

  Hereinafter, an anisotropic conductive film obtained by forming the anisotropic conductive adhesive of the present invention into a film will be described in detail. In addition, the anisotropic conductive adhesive of this invention is not limited to an anisotropic conductive film, An anisotropic conductive paste is also included.

  As shown in FIG. 1, the film-like anisotropic conductive adhesive 10 of the present invention is in an insulating adhesive 1 containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. Insulating coated magnetic conductive particles 2 are dispersed. Further, the magnetic conductive material having an average particle diameter of 1 to 10% with respect to the average particle diameter of the insulating coated magnetic conductive particles and magnetized after demagnetizing treatment The fine particles 3 are contained in an amount of 5 to 70 parts by mass with respect to a total of 100 parts by mass of the film-forming resin, the liquid epoxy compound, the epoxy curing agent, and the silane coupling agent.

  The magnetic conductive fine particles 3 magnetized after the demagnetization treatment are used in the liquid composition for forming an anisotropic conductive film used when forming the anisotropic conductive adhesive 10 into a film shape, or anisotropically. In the insulating adhesive that flows during the thermocompression bonding of the conductive connection, it adheres to the surface of the insulating coated magnetic conductive particles 2 by a magnetic force to form a conductive protrusion. As a result, the anisotropic conductive bonding of the anisotropic conductive adhesive 10 sufficiently penetrates into the surface of the electrode to be anisotropically conductive by thermocompression bonding. It is possible to break through the immobilization film on the surface of the electrode to be electrically conductively connected. Therefore, the connection resistance of the anisotropic conductive connection can be lowered.

  On the other hand, the insulation resistance in the direction orthogonal to the anisotropic conductive connection direction (that is, the plane direction of the anisotropic conductive film) adjusts the size and blending amount of the magnetic conductive fine particles 3, and the insulation coated magnetic conductive particles 2 Since it is localized on the surface, it is possible to prevent a decrease in the insulation resistance value in the direction orthogonal to the anisotropic conductive connection direction (that is, the plane direction of the anisotropic conductive film).

<Magnetic conductive fine particles 3 constituting anisotropic conductive adhesive>
Examples of magnetic materials for the magnetic conductive fine particles 3 include ferromagnets (Curie temperatures) such as Co (1115 ° C.), Fe (770 ° C.), Ni (350 ° C.), MnBi (357 ° C.), MnSb (314 ° C.), etc. Is mentioned. As ferrimagnetic materials, CrO ₂ (130 ° C.), FeOFe ₂ O ₃ (585 ° C.), NiOFe ₂ O ₃ (585 ° C.), CuOFe ₂ O ₃ (455 ° C.), MgOFe ₂ O ₃ (440 ° C.), MnOFe ₂ O ₃ (300 ° C.) and the like. Also, MK magnets, alnico magnets, rare earth magnets, etc., which are referred to as permanent magnets, can be used. In addition, Ti, ceramic, Zn, W, etc. which are paramagnetic substances can also be used.

  These magnetic conductive fine particles 3 may form an insulating film on the surface of the fine particles as long as they exhibit conductivity under anisotropic conductive connection conditions. In that case, an insulating resin or metal oxide film can be used as the insulating film. These insulating films can be formed by a known method. In particular, when the magnetic conductive fine particles are magnetic metal or alloy fine particles, an oxide film of the metal or alloy may be formed on the surface of the fine particles. In this case, the formation of the oxide film can be promoted by heating the magnetic conductive fine particles in an oxygen-containing environment.

  Particularly preferable examples of such magnetic conductive fine particles 3 include nickel fine particles in view of ferromagnetism, excellent element stability, and ease of demagnetization. In this case, a nickel oxide film may be formed on the ferromagnetic conductive fine particles 3 as an insulating film. If such a nickel oxide film is excessively thick, conductivity cannot be ensured in anisotropic conductive connection. Therefore, it is preferably 3 nm or less.

  Further, the average particle diameter of the magnetic conductive fine particles 3 greatly depends on the relative size relationship with the insulating coated magnetic conductive particles 2, and if it is too small, the bite into the surface of the electrode to be anisotropically conductive is small. Therefore, there is a concern that the connection resistance value is increased. On the other hand, if it is too large, the insulation resistance value in the direction perpendicular to the anisotropic conductive connection direction (the plane direction of the anisotropic conductive film) tends to decrease. The average particle diameter of the insulating coated magnetic conductive particles 2 is 1 to 10%, preferably 2 to 6%. The specific range of the average particle diameter is preferably 0.05 to 0.5 μm, more preferably 0.1 to 0.3 μm.

  If the content of the magnetic conductive fine particles 3 in the anisotropic conductive adhesive is too small, the conductive protrusions of the insulating coated magnetic conductive particles 2 are reduced, and the connection resistance value during anisotropic conductive connection tends to increase. On the other hand, even if the amount is too large, the entire surface of the insulating coated magnetic conductive particle 2 is covered with the magnetic conductive fine particles 3, and as a result, there are fewer conductive protrusions. Since the resistance value tends to increase and the insulation resistance value in the direction perpendicular to the anisotropic conductive connection direction (the plane direction of the anisotropic conductive film) tends to decrease, a film-forming resin as will be described later The total amount of the liquid epoxy compound, the epoxy curing agent and the silane coupling agent is preferably 5 to 70 parts by mass, more preferably 20 to 50 parts by mass.

  In the present invention, the magnetic conductive fine particles 3 are those that have been demagnetized and then magnetized before adjusting the anisotropic conductive adhesive. First, the reason why the demagnetization process is performed first is that when the magnetic conductive fine particles 3 are magnetized in advance, the magnetic moments of the magnetic domains in the magnetic conductive fine particles 3 can be easily aligned in a certain direction. This is because it can be efficiently magnetized. The reason why the magnetizing process is performed is to adhere to the surface of the insulating coated magnetic conductive particles 2 by magnetism.

  In addition, there is no restriction | limiting in particular as a method of the demagnetization process of the magnetic electroconductive fine particles 3, A well-known method can be used. For example, the magnetic conductive fine particles 3 may be demagnetized by heating to the Curie temperature or higher.

  In addition, when demagnetizing treatment is performed at a temperature lower than the Curie temperature, it is preferable to perform demagnetizing treatment so that the relative positional relationship between the magnetic conductive fine particles 3 does not fluctuate. Specifically, as shown in FIG. 2, the magnetic conductive fine particles 21 are put into a container 22 having an opening 22 a, and then pressed by a pressing means 23 inserted into the container 22 from the opening 22 a of the container 22. Then, the container 22 is temporarily fixed, and the container 22 is moved away from the demagnetizing coil at least once in the direction of the arrow while attenuating the magnetic field strength in the demagnetizing magnetic field formed by the demagnetizing coil 24. Thus, the demagnetization process can be performed. In order to increase the efficiency of the demagnetization process, the container 22 may be reciprocated (moved a plurality of times). The container 22 is not limited to a container having an opening. For example, the container 22 is preferably used even when the container is filled with magnetic conductive fine particles and then the opening is sealed by vacuum sealing. it can.

  The container 22 used in the demagnetization method is formed from a nonmagnetic material, a material with low magnetic permeability, or the like, and examples thereof include a glass container, an alumina container, and a porcelain container. The shape of the container is preferably a cylindrical shape, particularly a cylindrical shape, but may be a polygonal cylindrical shape. The bottom is preferably round. Moreover, the bottom part may be openable and closable.

  There is no restriction | limiting in particular as the press means 23, For example, the structure which presses the flat plate 23a which shows hard or elasticity with the pusher 23b may be sufficient. The level of pressing is a level that does not damage the magnetic powder to be demagnetized and can suppress the movement of the magnetic powder during the demagnetization process. The type, size, shape, and demagnetization of the magnetic powder. It can be determined according to the magnetic conditions.

  When the demagnetization treatment is performed at a temperature lower than the Curie temperature, as shown in FIG. 3, the magnetic conductive fine particles 31 are put into a liquid 33 in a container 32, and then the liquid 33 is solidified and temporarily fixed in a solidified product. The demagnetizing process is performed by moving the container 32 in the demagnetizing magnetic field formed by the demagnetizing coil 34 so as to move away from the demagnetizing coil at least once in the direction of the arrow while attenuating the magnetic field strength. You can also Further, the container 32 may be reciprocated (moved a plurality of times) in order to increase the efficiency of the demagnetization process. In this case, the liquid 33 is usually solidified in the container 32, but the container can be removed in the demagnetization process after the solidification. Moreover, it is preferable to solidify the liquid after introducing the magnetic conductive fine particles into the liquid and then performing a defoaming treatment. This is because if the bubbles are not defoamed, the bubbles are also taken into the coagulated product when the liquid is coagulated, and the magnetic conductive fine particles 31 in the vicinity of the bubbles can easily move.

  As a specific method for solidifying the liquid, there is a method of solidifying the liquid by cooling it below its freezing point. As the liquid, water, alcohols such as ethanol, alkanes such as hexane and cyclohexane, aryls such as toluene and naphthalene, and the like can be used. As a specific example of solidification, when water is used as the liquid, it can be solidified by cooling to 0 ° C. or lower. When cyclohexane (melting point: 7 ° C.) is used, cooling to 7 ° C. or less, preferably −10 ° C. can be mentioned. In this case, after the demagnetization treatment, the solidified material is allowed to stand or be heated until it reaches the solidification point of the liquid or more, and the demagnetized magnetic conductive fine particles 31 may be separated from the liquid by a conventional method.

  As another method for coagulating the liquid, there is a method in which a coagulant capable of coagulating the liquid is further blended into the liquid, and after the magnetic powder is charged, the liquid is coagulated with the coagulant. . For example, a method of using a liquid gelling agent as a coagulant. Specifically, when the liquid is water, gelatin is used as a coagulant, the gelatin is heated and dissolved in water, magnetic powder is added to it, defoamed as necessary, and then cooled. Gelation is mentioned. In this case, since the gelatin-derived gel is reversible that disappears by heating, after the demagnetization treatment, the solidified material is heated to a temperature at which the gel disappears, and the demagnetized magnetic conductive fine particles 31 are obtained by a conventional method. What is necessary is just to isolate | separate from a liquid.

  In the present invention, when the magnetic conductive fine particles 3 (21, 31) are magnetized, the method is not particularly limited, and can be performed by applying a conventionally known magnetization method. Further, the demagnetizing device of FIG. 2 or 3 can be used as the magnetizing device by causing the demagnetizing coil to function as the magnetizing coil.

<Insulation-coated magnetic conductive particles 2 constituting an anisotropic conductive film>
The insulating coated magnetic conductive particles 2 used in the present invention are magnetizable conductive particles, at least a part of which is made of a magnetic material (for example, a ferromagnetic material or a paramagnetic material). Therefore, the insulating coated magnetic conductive particles 2 include cases where they are magnetized and demagnetized. Such insulating coated magnetic conductive particles 2 include not only the case where the entire conductive particles are formed of a single magnetic material, but also particles in which a thin film of magnetic material is formed on the surface of the conductive particles or insulating particles, Examples thereof include particles in which a nonmagnetic metal film is further formed on such a magnetic thin film, and particles in which a thin film of a nonmagnetic insulating resin is further formed on the outermost surface of these magnetic powders.

  Specific examples of magnetic powders that can be used as the insulating coated magnetic conductive particles 2 include powders of magnetic metals or magnetic alloys such as nickel, iron, iron oxide, chromium oxide, ferrite, cobalt, and sendust, solder, copper, and the like. Powders such as metal-coated resin particles with a thin film of magnetic material formed on the surface of magnetic conductive particles or insulating resin core particles, powders with a gold-plated thin film formed on those surfaces, or an insulating resin layer The powder etc. can be mentioned.

  Among these, the insulating coated magnetic conductive particles 2 include a nickel plating layer formed on the surface of the resin particles as the core, considering the manufacturing cost, deformation due to heating and pressurization at the time of connection, and an insulating resin. Preferred examples include coated resin core nickel plated particles.

  The resin particles to be the core are not particularly limited, but organic materials having heat resistance and chemical resistance, for example, thermoplastic resins such as polyamide, polyguanamine, polystyrene, and acrylic resin can be preferably used.

  Further, as the insulating resin for insulating coating, a known insulating thermoplastic resin used for this kind of insulating coated conductive particles, for example, polyolefin, polyester, acrylic resin, urethane resin, epoxy resin, etc. is applied. be able to. If the thickness of such an insulating coating resin layer is too thin, the insulating property tends to decrease, and if it is too thick, the conductivity tends to decrease. Therefore, the thickness is preferably 0.05 to 0.5 μm, more preferably 0. .1 to 0.4 μm.

  If the thickness of the nickel plating layer of the resin core nickel plating particles is too thin, it will be damaged during thermocompression bonding during anisotropic conductive connection, and the connection reliability of the anisotropic conductive film tends to be reduced. Since the insulating coated magnetic conductive particles 2 tend to aggregate when the anisotropic conductive film is formed, the thickness is preferably 10 to 300 nm, more preferably 50 to 200 nm.

  If the average particle diameter of the insulating coated magnetic conductive particles 2 used in the present invention is too small, the ratio of the magnetic metal in the entire magnetic conductive particles becomes high, so that it is easily affected by magnetism. May occur, or the anisotropic conductive function of the conductive particles may be reduced, and the variation in the height of the terminal of the electronic component may not be followed. If it is too large, the insulating property between the wirings is lowered by the conductive particles, and the fine pitch connection itself tends not to be supported. Therefore, the thickness is preferably 0.5 to 10 μm, more preferably 2 to 5 μm.

  The insulating coated magnetic conductive particles 2 are demagnetized by the same method as the magnetic conductive fine particles 3 in order to prevent aggregation in the anisotropic conductive adhesive or the anisotropic conductive film forming composition. It is preferable to keep it.

  If the content of the insulating coated magnetic conductive particles 2 in the anisotropic conductive adhesive is too small, the connection reliability of the anisotropic conductive adhesive tends to decrease. If the content is too large, the anisotropic conductive is caused by thickening or aggregation. Since there is a tendency for handling properties to deteriorate during connection and the production of anisotropic conductive films tends to be hindered, the total of film-forming resins, liquid epoxy compounds, epoxy curing agents and silane coupling agents as described below Preferably it is 10-80 mass parts with respect to 100 mass parts, More preferably, it is 20-50 mass parts.

  Further, the mass blending ratio of the insulating coated magnetic conductive particles 2 and the magnetic conductive fine particles 3 is such that if the amount of the insulating coated magnetic conductive particles 2 is too large relative to the magnetic conductive fine particles 3, the magnetic conductive fine particles adhere around the insulating coated magnetic conductive particles. However, if the amount is too small, too much magnetic conductive fine particles adhere to the periphery of the insulating coated magnetic conductive particles, so that the insulating property tends to decrease. To 7: 8 (= [insulation-coated magnetic conductive particles: magnetic conductive fine particles]), more preferably 18: 1 to 7: 5 (= [insulation-coated magnetic conductive particles: magnetic conductive fine particles]).

<Insulating adhesive 1 constituting anisotropic conductive adhesive>
The insulating adhesive 1 constituting the anisotropic conductive adhesive of the present invention contains a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent.

  Examples of the film-forming resin include phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, polyolefin resin, and the like. can do. Among these, a phenoxy resin can be preferably used from the viewpoint of film forming property, workability, and connection reliability.

  As the liquid epoxy compound, those having an epoxy equivalent (g / eq) of usually about 100 to 4000 and having two or more epoxy groups in the molecule are preferable. For example, a bisphenol A type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, an ester type epoxy compound, an alicyclic epoxy compound, or the like can be preferably used. These compounds include monomers and oligomers. Two or more of these can be used in combination.

  If the content of the liquid epoxy compound in the insulating adhesive is too small, the anisotropic conductive adhesive tends to be insufficiently cured during anisotropic conductive connection. Since there exists a tendency to fall, Preferably it is 20-60 mass parts with respect to 100 mass parts of film forming resin, More preferably, it is 40-60 mass parts.

  Examples of epoxy curing agents include anionic curing agents such as polyamines and imidazoles, cationic curing agents such as sulfonium salts, and latent curing agents such as phenolic curing agents.

  If the content of the epoxy curing agent in the insulating adhesive is too small, the anisotropic conductive adhesive tends to be insufficiently cured during anisotropic conductive connection. Therefore, it is preferably 20 to 60 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the liquid epoxy compound.

  Examples of the silane coupling agent include an epoxy silane coupling agent and an acrylic silane coupling agent. These silane coupling agents are mainly alkoxysilane derivatives.

  If the content of the silane coupling agent in the insulating adhesive is too small, the adhesive property of the anisotropic conductive adhesive during anisotropic conductive connection tends to decrease. Since there exists a tendency to fall, Preferably it is 0.5-5 mass parts with respect to a total of 100 mass parts of film forming resin and a liquid epoxy compound, More preferably, it is 0.5-2 mass parts.

  Insulating adhesives include silica, mica and other fillers, softeners, accelerators, anti-aging agents, colorants (pigments, dyes), antistatic agents, preservatives, crosslinking agents, organic solvents, An ion catcher agent etc. can be mix | blended.

<Manufacture of anisotropic conductive adhesive>
An anisotropic conductive adhesive in which insulating coating magnetic conductive particles are dispersed in an insulating adhesive containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. The magnetic conductive particles are demagnetized, and the magnetic conductive fine particles magnetized after the demagnetization treatment are combined into a total of 100 of a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. 5 to 70 parts by mass with respect to parts by mass, the magnetic conductive fine particles have an average particle size of 0.05 to 0.5 μm, and the average particle size is the average particle of the insulating coated magnetic conductive particles The anisotropic conductive adhesive of the present invention, which is 1 to 10% of the diameter, can be produced by a production method having the following steps (A) and (B). Below, it demonstrates for every process.

Process (A)
First, the insulating coated magnetic conductive particles are demagnetized, and the magnetic conductive fine particles are demagnetized and then magnetized. A known method can be applied as a method of demagnetization treatment or magnetization treatment. Further, when the magnetic conductive fine particles are magnetic metal or alloy fine particles, they may be demagnetized by heating to a temperature higher than the Curie temperature, or using a demagnetization / magnetization device as shown in FIG. 2 or FIG. Demagnetization and magnetization can also be performed. In addition, when the insulating coating magnetic conductive particles are resin core nickel plating particles, they should be demagnetized by other methods rather than heating above the Curie temperature.

Process (B)
Next, an insulating adhesive containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent was subjected to demagnetization-treated insulating coated magnetic conductive particles and magnetized after demagnetization. Magnetic conductive fine particles and, if necessary, an organic solvent are mixed and dispersed by a known method. Thereby, an anisotropic conductive adhesive can be obtained. Here, in many cases, in this mixing and dispersing process, the magnetic conductive fine particles adhere to the surface of the insulating coated magnetic conductive particles. Alternatively, the magnetically conductive fine particles magnetized after the demagnetization treatment may be adhered to the surface of the insulating coated magnetic conductive particles subjected to the demagnetization treatment, and then mixed with the insulating adhesive.

  The appearance of the magnetic conductive fine particles adhering to the surface of the insulating coated magnetic conductive particles can be observed with an electron microscope.

  The insulating adhesive may be prepared by previously mixing a film-forming resin, a liquid epoxy compound, a curing agent for epoxy, and a silane coupling agent. These components and the insulating coated magnetic conductive particles and magnetic conductive fine particles may be prepared. Further, if necessary, it may be prepared by mixing with an organic solvent at the same time. As a mixing method, a known mixing method can be used.

  As the organic solvent, a solvent such as toluene used in a known anisotropic conductive adhesive or anisotropic conductive film forming composition can be used. The amount used is appropriately determined according to the required viscosity and the like.

  In addition, when an anisotropic conductive adhesive is a film, it is preferable to implement the following processes (C) following a process (B).

Process (C)
An anisotropic conductive adhesive whose viscosity is adjusted by blending an organic solvent for film formation is applied to one side of the release substrate according to a known film formation method and dried. Thereby, an anisotropic conductive film can be formed.

  As the release substrate, a polyterephthalate film can be preferably used after a silicone release treatment. About the operation and conditions of application | coating and drying, the operation and conditions of application | coating and drying in the case of preparation of the conventional anisotropic conductive film are employable.

<Connection structure>
The anisotropic conductive adhesive of the present invention described above, preferably the anisotropic conductive film, is preferably applied when anisotropically conductively connecting the terminal of the first electronic component and the terminal of the second electronic component. can do. By this anisotropic conductive connection, a connection structure in which the terminals of the first electronic component and the terminals of the second electronic component are anisotropically conductive connected is obtained. Such a connection structure is also one embodiment of the present invention.

  As the first electronic component and the second electronic component, known electric elements such as light emitting elements, semiconductor chips, and semiconductor modules, flexible printed wiring boards, glass wiring boards, glass epoxy boards, and the like can be applied. The terminal may be a wiring, an electrode pad, or a bump formed from a known material such as copper, gold, aluminum, or ITO, and the size is not particularly limited.

  As specific examples of the connection structure of the present invention, what is referred to as COG (chip on glass), COF (chip on film), FOG (film on glass), FOB (Film on Board), or the like is preferably cited. Can do.

<Method for manufacturing connection structure>
The connection structure described above is anisotropic by arranging the above-mentioned anisotropic conductive adhesive, preferably an anisotropic conductive film, between the terminal of the first electronic component and the terminal of the second electronic component. By pressing the first electronic component against the second electronic component while heating the conductive conductive film, the terminals can be manufactured by anisotropic conductive connection. In this case, the pressing can be performed using a metal pressure bonder or an elastic bonder. About heating, a heating means may be provided in the stage in which the 1st electronic component or the 2nd electronic component is mounted, and it may heat by providing a heating means in a bonder.

  Hereinafter, the present invention will be specifically described by way of examples.

Reference examples, Examples 1-9, Comparative Examples 1-10
<Preparation of anisotropic conductive film>
Magnetic conductive particles (average particle diameter of 4 μm (Bright 20GNR, Nippon Chemical Industry Co., Ltd.)) with a 100 nm thick electroless nickel plating layer formed on the resin core, and bisphenol A type phenoxy resin (YP50, new) Nippon Steel Chemical Co., Ltd.), a bisphenol A epoxy compound (EP828, Mitsubishi Chemical Co., Ltd.), an imidazole-based curing agent (Novacure 3941HP, Asahi Kasei Chemical Co., Ltd.), and a silane coupling agent (liquid epoxy compound component) A-187, Momentive Performance Materials LLC) and magnetic conductive fine particles (nickel fine particles) are mixed at a blending ratio shown in Tables 1 and 2 so that the solid content is 50% by mass with toluene. Thus, a composition for forming an anisotropic conductive film was prepared. This composition was applied to a peeled polyethylene terephthalate film having a thickness of 50 μm with a bar coater so as to have a dry thickness of 25 μm, and dried in an oven at 80 ° C. for 5 minutes to prepare an anisotropic conductive film.

  In addition, a reference example is an example which produced the anisotropic conductive film and the connection structure similarly to Example 1 except not using magnetic electroconductive fine particles.

<Pretreatment of magnetic conductive particles>
For the magnetic conductive particles (Bright 20GNR) which are the mother particles, those having an insulating coating as described below and those not having an insulating coating are prepared, as shown in Tables 1 and 2, They were used properly according to examples and comparative examples.

(Formation of insulation coating on magnetic conductive particles)
Using a resin coating device for particles (manufactured by Sony Chemical & Information Device Co., Ltd.), the surface of the magnetic conductive particles was coated with acrylic acid / styrene copolymer (PP-2000S, Dainippon Ink & Chemicals, Inc.). The insulating coating thickness after thermosetting was 0.2 μm.

  Insulating coated magnetic conductive particles were prepared with and without demagnetization treatment, and were used properly according to Examples and Comparative Examples as shown in Tables 1 and 2.

(Demagnetization treatment of insulating coated magnetic conductive particles)
Demagnetization processing was performed at a demagnetization speed of 1 mm / second and a magnetic field strength of 400 G using the magnetizing / demagnetizing apparatus (manufactured by Sony Chemical & Information Device Co., Ltd.) shown in FIG.

<Pretreatment of magnetic conductive fine particles>
For the magnetic conductive fine particles (Ni fine particles) that are the child particles, those having an insulating coating as described below and those not having an insulating coating are prepared, and as shown in Tables 1 and 2, Examples and It was used properly according to the comparative example.

(Formation of insulation coating on magnetic conductive fine particles)
Using a resin coating device for particles (manufactured by Sony Chemical & Information Device Co., Ltd.), the surface of the magnetic conductive fine particles was coated with an acrylic acid / styrene copolymer (PP-2000S, Dainippon Ink & Chemicals, Inc.). The insulating coating thickness was 5 nm.

  Further, as described below, the magnetic conductive fine particles with or without insulation coating are subjected to demagnetization treatment and then subjected to magnetization treatment without demagnetization treatment. As shown in Table 1 and Table 2, they were properly used according to the examples and comparative examples.

(Demagnetization treatment / magnetization treatment of magnetic conductive fine particles)
Demagnetization processing was performed at a demagnetization speed of 1 mm / second and a magnetic field strength of 400 G using the magnetizing / demagnetizing apparatus (manufactured by Sony Chemical & Information Device Co., Ltd.) shown in FIG. Thereafter, using the same magnetizing / demagnetizing device, the particles were left for 10 seconds without moving at a magnetic field strength of 400 G, and then the power of the demagnetizing device was turned off to perform the magnetizing process.

(Magnetic treatment of magnetic conductive fine particles)
Using the magnetizing / demagnetizing device shown in FIG. 1 (manufactured by Sony Chemical & Information Device Co., Ltd.), without demagnetizing, leaving the particles at a magnetic field strength of 400 G for 10 seconds, leaving the magnet The magnetizing process was performed by cutting off the power source.

<Creating a connection structure>
Further, the obtained anisotropic conductive film is formed with a glass wiring board electrode having the following electrodes and a gold bump (length 85 μm × width 30 μm × height 15 μm, bump pitch: 35 μm, space between bumps 10 μm). The connection structure was obtained by placing between the bumps of the IC chip (1.8 mm × 20 mm, 0.5 mm thickness) and heating and pressing with a flip chip bonder at 190 ° C. and 60 MPa for 10 seconds.

(Glass wiring board electrode material)
ITO: Poly (indium tin oxide), surface roughness Ra = about 10.0 nm, surface resistance = 10Ω / □
α-ITO: amorphous (indium tin oxide), surface roughness Ra = about 1.0 nm, surface resistance = 10Ω / □
IZO: Indium zinc oxide, surface roughness Ra = about 2.0 nm, surface resistance = 10Ω / □
Ti: Niobium-added titanium dioxide, surface roughness Ra = about 10.0 nm, surface resistance = 5Ω / □

<Evaluation>
About the obtained connection structure, the "connection resistance" and the "insulation resistance" were measured and evaluated as described below. Further, the amount of the insulating coated magnetic conductive particles biting into the electrode of the glass substrate was determined as follows. The obtained results are shown in Tables 1 and 2.

(Connection resistance evaluation)
The conduction resistance value of the obtained connection structure was measured by a four-terminal method (input current 1 mA) and evaluated according to the following evaluation criteria. In practice, the evaluation rank is desirably A or B.

Rank Contents A: Connection resistance value is less than 10Ω B: Connection resistance value is 10Ω or more and less than 50Ω C: Connection resistance value is 50Ω or more and less than 100Ω D: Connection resistance value is 100Ω or more

(Insulation resistance evaluation)
The resistance value between adjacent lines of the obtained connection structure was measured by measuring the insulation resistance value (applied voltage: 30 V) and evaluated according to the following evaluation criteria. In practice, the evaluation rank is desirably A or B.

Rank Contents A: Insulation resistance value is 1 × 10 ⁹ Ω or more B: Insulation resistance value is 1 × 10 ⁸ Ω or more and less than 1 × 10 ⁹ Ω C: Insulation resistance value is 1 × 10 ⁷ Ω or more and less than 1 × 10 ⁸ Ω D: Insulation resistance value is less than 1 × 10 ⁷ Ω

(Measurement of bite amount)
After anisotropic conductive adhesion, the amount (nm) of magnetic conductive fine particles adhering to the surface of the insulating coated magnetic conductive particles to the electrode on the glass substrate side was measured with a scanning electron microscope (S-4700, Hitachi, Ltd.). ) And read from the observed image. In addition, the observation sample was prepared by carrying out the cross-section cutting process of the mounting product sample. Practically, the amount of bite varies depending on the material, but is desirably 30 nm or more.

  As can be seen from Table 1, the insulation resistance evaluation of the connection structure using the anisotropic conductive film of the reference example not containing the magnetic conductive fine particles was A evaluation, but the amount of biting into the electrode of the glass substrate ( 5 or 10 nm) was small, and the connection resistance evaluation was C or D evaluation.

  On the other hand, in the case of the connection structure using the anisotropic conductive films of Examples 1 to 9 of the present invention, the connection resistance evaluation and the insulation resistance evaluation were both A or B evaluation. Moreover, all bite amount was 35 nm or more.

  On the other hand, the connection structure using the anisotropic conductive films of Comparative Examples 1 and 2 in which the blending amount of the magnetic conductive fine particles is relatively large with 80 parts by mass or more with respect to 100 parts by mass of the insulating adhesive component. In this case, the connection resistance evaluation was A or B evaluation, but the insulation resistance evaluation was C or D evaluation.

  In the case of the connection structure using the anisotropic conductive films of Comparative Examples 3 and 4 in which the average particle diameter of the magnetic conductive fine particles is relatively large as 0.7 μm or more, there is no A evaluation in connection resistance evaluation, and insulation Resistance evaluation was C or D evaluation. Moreover, the amount of biting was also reduced compared to the examples.

  In the case of the connection structure using the anisotropic conductive film of Comparative Examples 5 and 6 using the anisotropic conductive film in which the magnetic conductive particles are not coated with insulation, the insulation resistance evaluation was D evaluation.

  In the case of the connection structure using the anisotropic conductive films of Comparative Examples 7 and 8 using the magnetic conductive fine particles subjected to the magnetizing process without performing the demagnetizing process, the insulation resistance evaluation was C evaluation. .

  The insulation resistance evaluation of the connection structures using the anisotropic conductive films of Comparative Examples 8 to 10 using the insulating coated magnetic conductive particles not subjected to demagnetization treatment was C evaluation.

  The anisotropic conductive adhesive according to the present invention exhibits good connection reliability and insulation reliability. Therefore, it is useful when an electronic component is anisotropically conductively connected to a substrate.

DESCRIPTION OF SYMBOLS 1 Insulating adhesive 2 Insulation covering magnetic conductive particle 3, 21, 31 Magnetic conductive fine particle 10 Anisotropic conductive adhesive (anisotropic conductive film)
22, 32 Container 22a Opening 23 Pressing means 23a Flat plate 23b Pushers 24, 34 Demagnetizing coil 33 Liquid

Claims (12)

  An anisotropic conductive adhesive in which insulating coating magnetic conductive particles are dispersed in an insulating adhesive containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. The magnetic conductive particles are demagnetized, and the magnetic conductive fine particles magnetized after the demagnetization treatment are combined into a total of 100 of a film-forming resin, a liquid epoxy compound, an epoxy curing agent, and a silane coupling agent. 5 to 70 parts by mass with respect to parts by mass, the magnetic conductive fine particles have an average particle size of 0.05 to 0.5 μm, and the average particle size is the average particle of the insulating coated magnetic conductive particles An anisotropic conductive adhesive characterized by being 1 to 10% of the diameter.   The anisotropic conductive adhesive according to claim 1, wherein the insulating coated magnetic conductive particles are particles in which a nickel plating layer is formed on the surface of the resin particles serving as a core and are further coated with an insulating resin.   The anisotropic conductive adhesive according to claim 1 or 2, wherein the insulating coated magnetic conductive particles have an average particle diameter of 2 to 5 µm.   The anisotropic conductive adhesive according to claim 2, wherein the thickness of the nickel plating layer of the insulating coating magnetic conductive particles is 50 to 200 μm.   The anisotropic conductive adhesive according to claim 1, wherein the magnetic conductive fine particles are nickel fine particles.   The insulating coating magnetic conductive particles are contained in 10 to 80 parts by mass with respect to a total of 100 parts by mass of the film-forming resin, the liquid epoxy compound, the epoxy curing agent and the silane coupling agent. Anisotropic conductive adhesive.   The mass blending ratio of the insulating coated magnetic conductive particles and the magnetic conductive fine particles is 20: 1 to 7: 8 (= [insulating coated magnetic conductive particles: magnetic conductive fine particles]). Isotropic conductive adhesive. It is a manufacturing method of the anisotropic conductive adhesive of Claims 1-7, Comprising: The following processes (A) and (B):
Process (A)
A step of demagnetizing the insulating coated magnetic conductive particles, and a step of magnetizing the magnetic conductive fine particles after demagnetizing; and step (B)
Insulating coated magnetic conductive particles demagnetized to an insulating adhesive containing a film-forming resin, a liquid epoxy compound, an epoxy curing agent and a silane coupling agent, and magnetic conductive fine particles magnetized after the demagnetization treatment The manufacturing method which has the process of mixing and dispersing. When the anisotropic conductive adhesive is a film, following the step (B), the following step (C):
Process (C)
The manufacturing method of Claim 8 which has a process of apply | coating an anisotropic conductive adhesive to the single side | surface of a peeling base material, and forming an anisotropic conductive film by drying.   10. The method according to claim 8, wherein when the magnetic conductive fine particles are fine particles of a magnetic metal or alloy, the demagnetization treatment is a heat treatment of the magnetic metal or alloy fine particles to a Curie temperature or higher.   A connection structure in which a terminal of the first electronic component and a terminal of the second electronic component are anisotropically conductively connected by the anisotropic conductive agent according to any one of claims 1 to 7. body.   A method for manufacturing a connection structure in which a terminal of a first electronic component and a terminal of a second electronic component are connected, wherein the terminal is connected between the terminal of the first electronic component and the terminal of the second electronic component. By arranging the anisotropic conductive agent according to any one of claims 1 to 7 and pressing the first electronic component against the second electronic component while heating the anisotropic conductive agent, the terminals are connected to each other. A method for manufacturing a connection structure, characterized by anisotropic conductive connection.

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